6-(1-Hydro­xy-2,2-di­phenyl­ethyl)-4,4-di­phenyl-2-cyclo­hexen-1-one

The crystal structure of the title compound, C₃₂H₂₈O₂, (I), confirms the erythro stereochemistry of the aldol adduct. In the crystal, (I) forms centrosymmetric O—H...O=C hydrogen-bonded dimers which in turn are connected by C—H...O and C—H...π interactions.

S1. Comment

During studies of the crystal structure of 4,4-diphenyl-2,5-cyclohexadien-1-one (Anthony et al., 1998), the title compound, (I), was obtained as a by-product in the base-catalysed condensation of diphenylacetaldehyde with methyl vinyl ketone (Zimmerman et al., 1968) (see scheme). The chemical structure is consistent with (I) based on its NMR and IR spectra. The stereochemistry of (I) was established by X-ray diffraction and confirmed to be erythro at C2 and C19 stereogenic centres. The ready reversibility of aldol condensation under the equlibrium conditions of alcoholic KOH medium provides the expected erythro diastereomer (House, 1972). The molecular geometry of (I) in the crystal is shown in Fig. 1 (Johnson, 1976). \sch

In the crystal, inversion-related molecules of (I) form O—H···O=C dimers, (II), in the (110) layer between the hydroxy group and the carbonyl oxygen atom [O2—H2A···O1 1.90 (2) Å, 176.6 (15)°] (Fig. 2). Such dimers are in turn connected by C—H···O and C—H..π interactions (Desiraju & Steiner, 1999) along [100] from the phenyl and olefin H atoms to the carbonyl and phenyl (C21—C26) acceptor groups, respectively, [C29—H29A···O1 2.59 Å, 161.4°; C5—H5A···π(centroid) 2.73 Å, 170.0°]. The chains are interlinked by (phenyl)C—H···O(hydroxyl) interactions along [010] [C16—H16A···O2: 2.51 Å, 132.5°], not shown in Fig.2.

Allen et al. (1999) have reported on the probabilities of formation of cyclic hydrogen bond intermolecular motifs in organic crystal structures archived in the Cambridge Structural Database. Supramolecular synthon (II) occurs in 20 structures out of a possible 282 molecules that contain the β-hydroxy carbonyl functional group, giving it a probability of formation (P_s) of 0.07. While the P_s of motif (II) is low and its overall ranking 71/75 in the CSD analysis, it may be noted that the occurrence of this synthon is more frequent in crystal structures of aldol adducts (Fair et al., 1985; Gleiter et al., 1996; Gross & Finn, 1994; Lodge & Heathcock, 1987).

S2. Experimental

(I) was synthesized as shown in the scheme (Zimmerman et al., 1968). Colorless crystals were obtained upon recrystallization from 5% ethyl acetate/hexane (m.p. 457 K).

S3. Refinement

The data collection is 93.4% complete; some of the highest angle regions were not completely measured because the reflections were very weak. The hydroxyl hydrogen atom was identified from a Fourier synthesis and refined freely. Hydrogen atoms bonded to carbon were generated at idealized geometries and isotropically refined using a riding model.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1976) and PLUTON (Spek, 1992); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. ORTEPII (Johnson, 1976) diagram and atom numbering scheme for (I); displacement ellipsoids are drawn at 50% probability level for non-H atoms.
	Fig. 2. View of (I) in (101) to show the centrosymmetric O—H···O dimer, (II), and the intermolecular C—H···O and C—H···π interactions.

4,4-Diphenyl-6-(2,2-diphenyl-1-hydroxyethyl)-2-cyclohexen-1-one

Crystal data

C32H28O2	F(000) = 472
Mr = 444.54	Dx = 1.228 Mg m^−3
Triclinic, P1	Melting point: 457 K K
a = 9.6111 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5199 (12) Å	Cell parameters from 1500 reflections
c = 11.5621 (12) Å	θ = 1.9–21.5°
α = 84.458 (1)°	µ = 0.08 mm^−1
β = 77.829 (1)°	T = 168 K
γ = 74.138 (1)°	Prism, colorless
V = 1202.7 (2) Å^3	0.5 × 0.31 × 0.15 mm
Z = 2

Data collection

CCD area detector diffractometer	3460 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 26.4°, θmin = 2.8°
ϕ and ω scans	h = −5→11
10624 measured reflections	k = −14→14
4605 independent reflections	l = −13→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0549P)^2] where P = (Fo^2 + 2Fc^2)/3
4605 reflections	(Δ/σ)max = 0.001
337 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.18 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
O2	0.21625 (9)	0.79715 (8)	0.03529 (7)	0.0288 (2)
H2A	0.1288 (19)	0.8523 (15)	0.0596 (14)	0.060 (5)*
O1	0.05489 (9)	1.03957 (7)	−0.12311 (8)	0.0323 (2)
C3	0.15696 (12)	0.71694 (10)	−0.17797 (10)	0.0256 (3)
H3A	0.1077	0.6939	−0.0984	0.036 (3)*
H3B	0.2502	0.6540	−0.2004	0.027 (3)*
C19	0.28497 (12)	0.83579 (11)	−0.07771 (10)	0.0240 (3)
H19A	0.2960	0.9189	−0.0726	0.024 (3)*
C4	0.05652 (12)	0.72143 (10)	−0.26778 (10)	0.0249 (3)
C27	0.52557 (12)	0.73911 (10)	−0.00771 (10)	0.0250 (3)
C1	0.05312 (12)	0.94094 (10)	−0.15400 (10)	0.0244 (3)
C2	0.19215 (12)	0.83778 (10)	−0.17246 (10)	0.0238 (3)
H2B	0.2525	0.8536	−0.2511	0.027 (3)*
C6	−0.08175 (12)	0.92091 (11)	−0.17872 (10)	0.0265 (3)
H6A	−0.1729	0.9789	−0.1550	0.027 (3)*
C13	0.00807 (12)	0.60287 (10)	−0.25498 (10)	0.0254 (3)
C20	0.43922 (12)	0.74738 (11)	−0.10649 (10)	0.0248 (3)
H20A	0.4228	0.6657	−0.1088	0.024 (3)*
C5	−0.08047 (12)	0.82387 (11)	−0.23345 (10)	0.0266 (3)
H5A	−0.1702	0.8185	−0.2520	0.031 (3)*
C21	0.52382 (12)	0.77360 (12)	−0.22888 (11)	0.0299 (3)
C18	−0.07550 (13)	0.57393 (11)	−0.14721 (11)	0.0303 (3)
H18A	−0.0977	0.6257	−0.0829	0.036 (4)*
C7	0.13479 (13)	0.74501 (11)	−0.39505 (10)	0.0274 (3)
C28	0.60319 (13)	0.82251 (12)	0.00076 (11)	0.0316 (3)
H28A	0.5996	0.8897	−0.0541	0.038 (4)*
C14	0.03896 (13)	0.52476 (11)	−0.34693 (11)	0.0301 (3)
H14A	0.0961	0.5421	−0.4209	0.033 (3)*
C15	−0.01239 (14)	0.42189 (12)	−0.33222 (12)	0.0352 (3)
H15A	0.0096	0.3698	−0.3962	0.050 (4)*
C16	−0.09516 (14)	0.39447 (12)	−0.22538 (12)	0.0352 (3)
H16A	−0.1303	0.3239	−0.2156	0.041 (4)*
C17	−0.12642 (14)	0.47109 (12)	−0.13265 (12)	0.0335 (3)
H17A	−0.1831	0.4529	−0.0587	0.042 (4)*
C22	0.52315 (13)	0.89082 (13)	−0.27422 (12)	0.0362 (3)
H22A	0.4712	0.9576	−0.2264	0.042 (4)*
C12	0.06060 (15)	0.82371 (11)	−0.47428 (11)	0.0351 (3)
H12A	−0.0398	0.8655	−0.4489	0.037 (4)*
C32	0.53036 (14)	0.64335 (11)	0.07555 (11)	0.0324 (3)
H32A	0.4767	0.5861	0.0722	0.036 (4)*
C23	0.59737 (15)	0.91107 (17)	−0.38812 (13)	0.0495 (4)
H23A	0.5956	0.9912	−0.4176	0.064 (5)*
C29	0.68620 (14)	0.80874 (13)	0.08883 (12)	0.0380 (3)
H29A	0.7393	0.8662	0.0931	0.048 (4)*
C26	0.60352 (13)	0.67787 (14)	−0.30046 (12)	0.0405 (3)
H26A	0.6073	0.5973	−0.2713	0.040 (4)*
C8	0.28133 (15)	0.68630 (15)	−0.43600 (12)	0.0482 (4)
H8A	0.3348	0.6315	−0.3841	0.068 (5)*
C30	0.69175 (14)	0.71249 (13)	0.16958 (12)	0.0403 (3)
H30A	0.7495	0.7027	0.2289	0.056 (4)*
C31	0.61263 (15)	0.63020 (12)	0.16366 (12)	0.0390 (3)
H31A	0.6145	0.5644	0.2201	0.052 (4)*
C25	0.67785 (16)	0.69880 (18)	−0.41447 (14)	0.0551 (5)
H25A	0.7319	0.6325	−0.4622	0.063 (5)*
C9	0.35127 (17)	0.70596 (17)	−0.55110 (14)	0.0572 (4)
H9A	0.4520	0.6654	−0.5767	0.079 (6)*
C11	0.13024 (18)	0.84235 (13)	−0.58962 (13)	0.0472 (4)
H11A	0.0768	0.8961	−0.6422	0.067 (5)*
C10	0.27585 (18)	0.78397 (14)	−0.62892 (13)	0.0484 (4)
H10A	0.3235	0.7971	−0.7080	0.062 (5)*
C24	0.67357 (16)	0.8148 (2)	−0.45844 (13)	0.0574 (5)
H24A	0.7228	0.8286	−0.5368	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0228 (4)	0.0345 (5)	0.0261 (5)	−0.0045 (4)	−0.0032 (3)	0.0005 (4)
O1	0.0267 (4)	0.0266 (5)	0.0435 (5)	−0.0052 (4)	−0.0080 (4)	−0.0034 (4)
C3	0.0231 (6)	0.0259 (6)	0.0283 (7)	−0.0042 (5)	−0.0088 (5)	−0.0012 (5)
C19	0.0203 (6)	0.0256 (6)	0.0273 (6)	−0.0073 (5)	−0.0055 (5)	−0.0006 (5)
C4	0.0219 (6)	0.0278 (6)	0.0263 (6)	−0.0071 (5)	−0.0074 (5)	0.0008 (5)
C27	0.0180 (5)	0.0275 (6)	0.0271 (6)	−0.0009 (5)	−0.0040 (5)	−0.0044 (5)
C1	0.0237 (6)	0.0263 (7)	0.0229 (6)	−0.0074 (5)	−0.0039 (5)	0.0020 (5)
C2	0.0192 (6)	0.0272 (6)	0.0248 (6)	−0.0058 (5)	−0.0037 (5)	−0.0009 (5)
C6	0.0190 (6)	0.0292 (7)	0.0289 (7)	−0.0033 (5)	−0.0042 (5)	0.0018 (5)
C13	0.0220 (6)	0.0292 (7)	0.0268 (6)	−0.0060 (5)	−0.0096 (5)	0.0000 (5)
C20	0.0205 (6)	0.0254 (6)	0.0292 (7)	−0.0050 (5)	−0.0075 (5)	−0.0011 (5)
C5	0.0210 (6)	0.0326 (7)	0.0276 (6)	−0.0085 (5)	−0.0082 (5)	0.0046 (5)
C21	0.0168 (6)	0.0438 (8)	0.0292 (7)	−0.0048 (5)	−0.0084 (5)	−0.0026 (6)
C18	0.0301 (7)	0.0332 (7)	0.0294 (7)	−0.0095 (5)	−0.0069 (5)	−0.0035 (5)
C7	0.0276 (6)	0.0306 (7)	0.0281 (7)	−0.0129 (5)	−0.0066 (5)	−0.0026 (5)
C28	0.0278 (6)	0.0338 (7)	0.0350 (7)	−0.0096 (5)	−0.0084 (5)	−0.0006 (6)
C14	0.0319 (6)	0.0328 (7)	0.0258 (7)	−0.0082 (5)	−0.0073 (5)	0.0003 (5)
C15	0.0436 (8)	0.0325 (7)	0.0329 (7)	−0.0109 (6)	−0.0129 (6)	−0.0030 (6)
C16	0.0400 (7)	0.0316 (7)	0.0399 (8)	−0.0155 (6)	−0.0150 (6)	0.0038 (6)
C17	0.0328 (7)	0.0382 (8)	0.0314 (7)	−0.0139 (6)	−0.0070 (6)	0.0043 (6)
C22	0.0245 (6)	0.0500 (9)	0.0344 (7)	−0.0105 (6)	−0.0084 (5)	0.0054 (6)
C12	0.0404 (8)	0.0306 (7)	0.0327 (7)	−0.0082 (6)	−0.0060 (6)	0.0011 (6)
C32	0.0340 (7)	0.0280 (7)	0.0351 (7)	−0.0059 (5)	−0.0090 (6)	−0.0019 (5)
C23	0.0318 (8)	0.0778 (12)	0.0415 (9)	−0.0211 (8)	−0.0127 (6)	0.0173 (8)
C29	0.0309 (7)	0.0458 (8)	0.0418 (8)	−0.0121 (6)	−0.0113 (6)	−0.0084 (6)
C26	0.0258 (7)	0.0547 (10)	0.0385 (8)	−0.0023 (6)	−0.0072 (6)	−0.0117 (7)
C8	0.0305 (7)	0.0748 (11)	0.0346 (8)	−0.0067 (7)	−0.0055 (6)	−0.0010 (7)
C30	0.0356 (7)	0.0484 (9)	0.0367 (8)	0.0002 (6)	−0.0177 (6)	−0.0092 (7)
C31	0.0446 (8)	0.0342 (8)	0.0343 (8)	0.0006 (6)	−0.0148 (6)	0.0016 (6)
C25	0.0280 (7)	0.0939 (14)	0.0392 (9)	−0.0064 (8)	−0.0010 (6)	−0.0227 (9)
C9	0.0338 (8)	0.0946 (13)	0.0410 (9)	−0.0187 (8)	0.0036 (7)	−0.0100 (9)
C11	0.0684 (10)	0.0382 (8)	0.0332 (8)	−0.0151 (8)	−0.0071 (7)	0.0052 (6)
C10	0.0603 (10)	0.0582 (10)	0.0322 (8)	−0.0340 (8)	0.0047 (7)	−0.0042 (7)
C24	0.0325 (8)	0.1091 (16)	0.0301 (8)	−0.0209 (9)	−0.0041 (6)	0.0028 (9)

Geometric parameters (Å, º)

O2—C19	1.4234 (14)	C21—C22	1.3994 (18)
O1—C1	1.2290 (14)	C18—C17	1.3839 (17)
C3—C2	1.5296 (16)	C7—C8	1.3876 (18)
C3—C4	1.5485 (15)	C7—C12	1.3896 (17)
C19—C20	1.5421 (16)	C28—C29	1.3930 (18)
C19—C2	1.5468 (15)	C14—C15	1.3864 (17)
C4—C5	1.5180 (16)	C15—C16	1.3806 (18)
C4—C7	1.5403 (16)	C16—C17	1.3860 (18)
C4—C13	1.5439 (16)	C22—C23	1.3904 (19)
C27—C28	1.3893 (16)	C12—C11	1.3854 (19)
C27—C32	1.3898 (17)	C32—C31	1.3894 (18)
C27—C20	1.5289 (15)	C23—C24	1.380 (2)
C1—C6	1.4655 (15)	C29—C30	1.376 (2)
C1—C2	1.5179 (16)	C26—C25	1.393 (2)
C6—C5	1.3327 (16)	C8—C9	1.386 (2)
C13—C14	1.3907 (17)	C30—C31	1.3820 (19)
C13—C18	1.3975 (17)	C25—C24	1.376 (2)
C20—C21	1.5236 (16)	C9—C10	1.380 (2)
C21—C26	1.3911 (18)	C11—C10	1.376 (2)
C2—C3—C4	112.58 (9)	C26—C21—C22	117.91 (12)
O2—C19—C20	106.31 (9)	C26—C21—C20	119.24 (12)
O2—C19—C2	111.06 (8)	C22—C21—C20	122.84 (11)
C20—C19—C2	112.08 (9)	C17—C18—C13	121.05 (11)
C5—C4—C7	109.88 (9)	C8—C7—C12	117.33 (12)
C5—C4—C13	107.74 (9)	C8—C7—C4	121.28 (11)
C7—C4—C13	111.94 (9)	C12—C7—C4	121.37 (11)
C5—C4—C3	106.84 (9)	C27—C28—C29	120.74 (12)
C7—C4—C3	111.01 (9)	C15—C14—C13	120.98 (12)
C13—C4—C3	109.26 (9)	C16—C15—C14	120.58 (12)
C28—C27—C32	118.22 (11)	C15—C16—C17	119.18 (12)
C28—C27—C20	122.45 (11)	C18—C17—C16	120.33 (12)
C32—C27—C20	119.31 (10)	C23—C22—C21	121.03 (14)
O1—C1—C6	121.01 (10)	C11—C12—C7	121.24 (13)
O1—C1—C2	120.93 (10)	C31—C32—C27	120.90 (12)
C6—C1—C2	118.01 (10)	C24—C23—C22	120.09 (16)
C1—C2—C3	111.49 (9)	C30—C29—C28	120.42 (12)
C1—C2—C19	110.71 (9)	C21—C26—C25	120.75 (15)
C3—C2—C19	112.73 (9)	C9—C8—C7	121.35 (14)
C5—C6—C1	122.01 (11)	C29—C30—C31	119.44 (12)
C14—C13—C18	117.88 (11)	C30—C31—C32	120.27 (13)
C14—C13—C4	123.28 (11)	C24—C25—C26	120.53 (15)
C18—C13—C4	118.81 (10)	C10—C9—C8	120.62 (14)
C21—C20—C27	113.48 (9)	C10—C11—C12	120.82 (14)
C21—C20—C19	112.38 (9)	C11—C10—C9	118.62 (14)
C27—C20—C19	111.58 (9)	C25—C24—C23	119.67 (14)
C6—C5—C4	123.57 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1^i	0.914 (18)	1.903 (18)	2.8163 (14)	176.6 (15)
C16—H16A···O2^ii	0.95	2.51	3.2325 (19)	133
C29—H29A···O1^iii	0.95	2.59	3.512 (2)	161
C5—H5A···π^iv	0.95	2.73	3.674	170

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