1,3-Di­phenyl-1-o-tolyl-3,4-di­methyl­indan

The title compound, C₃₀H₂₈, was prepared by tris-(2,4-di­bromo­phenyl)­aminium hexa­chloro­antimonate-induced cyclo­dimerization of 1-o-tolyl-1-phenyl­ethyl­ene in 1,1,1,3,3,3-hexa­fluoro­propan-2-ol. The X-ray analysis of the only product of the reaction confirms that it is the cis isomer.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.045
• wR factor = 0.057
• Data-to-parameter ratio = 8.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



THETM_01  Alert B The value of sine(theta_max)/wavelength is less than 0.575
          Calculated sin(theta_max)/wavelength =    0.5727

Author response: The sine(theta_max)/wavelength (0.5723) depends on the default limit of 120.00 for the two_theta_max.

 Alert Level C:



REFNR_01  Alert C Ratio of reflections to parameters is < 10 for a
          centrosymmetric structure
          sine(theta)/lambda                0.5727
          Proportion of unique data used    0.6858
          Ratio reflections to parameters   8.8450

General Notes



ABSTM_02  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      0.929
          Tmax scaled      0.929 Tmin scaled      0.865


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The hole catalyst tris(2,4-dibromophenyl)aminium hexachloroantimonate [2,4-Br₂C₆H₃)₃N⁺SbCl₆, A; E^red = 1.66 versus SCE; Baker et al., 1965] has been successfully employed for accomplishing novel, selective and highly efficient chemical transformations on a great variety of electron-rich substrates (Bauld, 1989; Nelsen, 1987; Lopez et al., 1994; Caló et al., 1995). Among them, we recently reported the facile aminium salt (A) induced cyclodimerization of several 1-aryl-1-phenylethylenes, leading, in dichloromethane solutions, to mixtures of two pairs of diastereoisomeric indan derivatives (Ciminale et al., 1996). On the contrary, a similar reaction, carried out in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFP) solution of 1-o-tolyl-1-phenylethylene, afforded only the cis isomer of the title compound, (I) (Lopez et al., unpublished results).

The crystal structure of (I) consists of discrete molecules of C₃₀H₂₈. The bond distances and angles are in agreement with accepted values. The atoms of the indan group, with the exception of C2, are almost coplanar, with an average deviation of 0.012 (3) Å. The conformation of the the five-membered ring of the indan group can be described as an envelope (Evans & Boeyens, 1989). The out-of-plane displacements from the least-squares plane are 0.121 (3), -0.148 (3), 0,120 (3), -0.049 (3) and -0.044 (3) Å for C1, C2, C3, C8 and C9, respectively. C2, at the apex, deviates from the best plane of the other four atoms by 0.371 (2) Å; this compares with an average distance for the other atoms of 0.002 (3) Å. This plane makes an angle of 23.8 (1)° with the C1/C2/C3 plane.

The phenyl rings are cis with respect to the indan group. The angle between their least-squares planes is 35.3 (1)°. The C3—C25 and C1—C19 bonds make angles of 44.5 (1) and 43.4 (1)°, respectively, with the best plane of the indan group, while bonds C3—C10 and C1—C19 form angles of 68.9 (2) and 66.8 (1)°. Furthermore, the distance between C19 and C25 is 4.717 (4) Å compared with a distance between C10 and C12 of 3.519 (4) Å, thus relieving steric strain between the two phenyl groups.

S2. Experimental

A catalytic amount of tris(2,4-dibromophenyl)ammoniumyl hexachloroantimonate (A; 0.105 g, 0.10 mmol) was added rapidly to a stirred HFP (10 ml) solution of 1-o-tolyl-1-phenylethylene (0.194 g, 1 mmol) at room temperature. The reaction mixture, whose intensely green colour faded slowly, was monitored by TLC (petroleum ether/ethyl acetate, 20:1) and by GC—MS spectrometry, revealing the total disappearance of the starting material within 6 h, and the simultaneous formation of the main reaction product with molecular peak m/z = 388. The excess of aminium salt was destroyed by addition of 2 ml of ethyl ether, then the reaction mixture was poured into 10 ml of water and extracted with ethyl ether (10 ml × 2). The organic phase was separated, dried over sodium sulfate and the solvent removed in vacuo. Column chromatography (silica gel, petroleum ether/ethyl acetate, 20:1) of the residue gave a pale-yellow crystalline product (0.175 g, 90%). Recrystallization from methanol furnished colourless crystals of pure cis-1,3-diphenyl-1-o-tolyl-3,4-dimethylindan: m.p. 448–449 K with elemental analysis consistent with C₃₀H₂₈; calculated: C 92.73, H 7.26%; found: C 92.87, H 7.16%; IR (KBr) 3055, 3020, 2967, 1492, 1444, 770, 758, 744, 731, 697, 637 cm^-1; ¹H NMR (500 MHz, CDCl₃): δ_H 7.36–6.63 (m, 17H), 3.53 (d, J = 13.8 Hz, 1H), 2.78 (d, J = 13.8 Hz, 1H), 1.91, (s, 3H), 1.53 (s, 3H), 1.42 (s, 3H) p.p.m.; ¹³C NMR (CDCl₃): δ_C 150.7, 149.6, 149.3, 148.3, 147.9, 147.6, 136.6, 134.5, 132.2, 129.9, 128.9. 128.4, 128.1, 127.1, 126.3, 125.9, 125.6, 125.5, 125.0, 60.9, 51.67, 24.4, 22.2, 18.9 p.p.m.; MS m/z (relATIVE abundance): 388 (M⁺, 20), 373 (11), 297 (100), 282 (19), 265 (13).

S3. Refinement

The poor data/parameter ratio of 8.85 is a result of the weak diffracting power of the crystal. The position of the H atoms were calculated geometrically at a distance of 0.96 Å from the corresponding C atom, and a riding model was used during their refinament. The orientation of the methyl H atoms was not refined.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Coorporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Coorporation, 1985); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CAOS (Camalli & Spagna, 1994); molecular graphics: CAOS; software used to prepare material for publication: CAOS.

Figures

	Fig. 1. Drawing of the title compound with the atom-numbering scheme. Displacement ellipsoids are at the 50% probability level.
	Fig. 2. The molecular packing in the unit cell.

(I)

Crystal data

C30H28	Z = 2
Mr = 388.55	F(000) = 416
Triclinic, P1	Dx = 1.163 Mg m^−3
a = 8.577 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.997 (3) Å	Cell parameters from 25 reflections
c = 12.327 (3) Å	θ = 29.2–38.9°
α = 92.56 (2)°	µ = 0.49 mm^−1
β = 93.38 (2)°	T = 293 K
γ = 106.67 (2)°	Prism, colourless
V = 1109.6 (5) Å^3	0.35 × 0.20 × 0.15 mm

Data collection

Rigaku AFC-5 four-circle diffractometer	2397 reflections with F > 6σ(F)
Radiation source: rotating-anode X-ray tube	Rint = 0.029
Graphite monochromator	θmax = 62.0°, θmin = 3.6°
θ/2θ scans	h = 0→9
Absorption correction: empirical (using intensity measurements) (North et al., 1968)	k = −12→12
Tmin = 0.931, Tmax = 1.000	l = −14→14
3828 measured reflections	3 standard reflections every 97 reflections
3495 independent reflections	intensity decay: none

Refinement

Refinement on F	271 parameters
Least-squares matrix: Full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	w = 1/(5.1485 + 0.0617*F + 0.0005*F^2)
wR(F^2) = 0.057	(Δ/σ)max < 0.001
S = 0.94	Δρmax = 0.23 e Å^−3
2397 reflections	Δρmin = −0.17 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3398 (3)	0.1115 (2)	0.3017 (2)	0.042 (1)
C2	0.3957 (3)	−0.0118 (2)	0.3059 (2)	0.049 (1)
C3	0.2968 (3)	−0.1083 (2)	0.2122 (2)	0.045 (1)
C4	0.0027 (3)	−0.1230 (2)	0.1281 (2)	0.046 (1)
C5	−0.1153 (3)	−0.0591 (2)	0.1181 (2)	0.051 (1)
C6	−0.0926 (3)	0.0601 (3)	0.1688 (2)	0.054 (1)
C7	0.0508 (3)	0.1199 (2)	0.2311 (2)	0.049 (1)
C8	0.1714 (3)	0.0587 (2)	0.2408 (2)	0.040 (1)
C9	0.1477 (3)	−0.0616 (2)	0.1912 (2)	0.040 (1)
C10	0.3934 (3)	−0.0935 (3)	0.1102 (2)	0.063 (1)
C11	−0.0300 (4)	−0.2536 (3)	0.0718 (2)	0.064 (1)
C12	0.4577 (3)	0.2113 (2)	0.2379 (2)	0.045 (1)
C13	0.6231 (3)	0.2637 (2)	0.2730 (2)	0.055 (1)
C14	0.7225 (3)	0.3515 (3)	0.2098 (3)	0.070 (1)
C15	0.6645 (4)	0.3885 (3)	0.1137 (3)	0.072 (1)
C16	0.5024 (4)	0.3390 (3)	0.0797 (2)	0.062 (1)
C17	0.4021 (3)	0.2516 (2)	0.1412 (2)	0.050 (1)
C18	0.7007 (3)	0.2321 (3)	0.3780 (2)	0.073 (1)
C19	0.3183 (3)	0.1667 (2)	0.4157 (2)	0.045 (1)
C20	0.3657 (3)	0.2959 (2)	0.4427 (2)	0.058 (1)
C21	0.3393 (4)	0.3435 (3)	0.5443 (3)	0.074 (1)
C22	0.2662 (4)	0.2633 (3)	0.6194 (2)	0.074 (1)
C23	0.2136 (4)	0.1354 (3)	0.5928 (2)	0.075 (1)
C24	0.2387 (4)	0.0871 (3)	0.4921 (2)	0.064 (1)
C25	0.2535 (3)	−0.2425 (2)	0.2519 (2)	0.047 (1)
C26	0.1382 (3)	−0.2770 (2)	0.3280 (2)	0.055 (1)
C27	0.0935 (4)	−0.3976 (3)	0.3659 (2)	0.067 (1)
C28	0.1661 (4)	−0.4864 (3)	0.3300 (3)	0.079 (1)
C29	0.2807 (5)	−0.4545 (3)	0.2559 (3)	0.088 (2)
C30	0.3254 (4)	−0.3337 (3)	0.2165 (3)	0.071 (1)
H1	0.5103	0.0083	0.2960	0.049*
H2	0.3745	−0.0479	0.3750	0.049*
H3	−0.2153	−0.0988	0.0748	0.052*
H4	−0.1766	0.1016	0.1607	0.053*
H5	0.0665	0.2022	0.2671	0.049*
H6	0.3323	−0.1529	0.0527	0.063*
H7	0.4123	−0.0084	0.0874	0.063*
H8	0.4961	−0.1097	0.1266	0.063*
H9	−0.1359	−0.2777	0.0333	0.065*
H10	0.0515	−0.2521	0.0213	0.065*
H11	−0.0260	−0.3140	0.1250	0.065*
H12	0.8355	0.3879	0.2340	0.070*
H13	0.7365	0.4479	0.0712	0.072*
H14	0.4591	0.3649	0.0140	0.062*
H15	0.2891	0.2170	0.1162	0.050*
H16	0.6202	0.1709	0.4139	0.072*
H17	0.7879	0.1974	0.3615	0.072*
H18	0.7430	0.3081	0.4249	0.072*
H19	0.4176	0.3536	0.3906	0.057*
H20	0.3733	0.4337	0.5616	0.074*
H21	0.2510	0.2962	0.6902	0.074*
H22	0.1594	0.0784	0.6447	0.075*
H23	0.2002	−0.0029	0.4746	0.064*
H24	0.0880	−0.2152	0.3551	0.055*
H25	0.0114	−0.4194	0.4171	0.067*
H26	0.1370	−0.5698	0.3571	0.078*
H27	0.3312	−0.5167	0.2303	0.089*
H28	0.4065	−0.3133	0.1645	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.043 (1)	0.039 (1)	0.044 (1)	0.011 (1)	−0.001 (1)	0.001 (1)
C2	0.044 (1)	0.043 (1)	0.058 (2)	0.012 (1)	−0.005 (1)	0.001 (1)
C3	0.045 (1)	0.046 (1)	0.045 (1)	0.015 (1)	0.004 (1)	0.000 (1)
C4	0.047 (1)	0.048 (1)	0.040 (1)	0.007 (1)	0.000 (1)	0.005 (1)
C5	0.043 (1)	0.062 (2)	0.047 (1)	0.013 (1)	−0.004 (1)	0.005 (1)
C6	0.044 (1)	0.063 (2)	0.058 (2)	0.022 (1)	0.003 (1)	0.012 (1)
C7	0.049 (1)	0.047 (1)	0.052 (1)	0.016 (1)	0.006 (1)	0.006 (1)
C8	0.040 (1)	0.038 (1)	0.042 (1)	0.011 (1)	0.004 (1)	0.005 (1)
C9	0.042 (1)	0.041 (1)	0.038 (1)	0.010 (1)	0.006 (1)	0.007 (1)
C10	0.062 (2)	0.069 (2)	0.064 (2)	0.023 (1)	0.020 (1)	0.005 (1)
C11	0.072 (2)	0.056 (2)	0.057 (2)	0.011 (1)	−0.013 (1)	−0.007 (1)
C12	0.047 (1)	0.040 (1)	0.045 (1)	0.010 (1)	0.003 (1)	−0.001 (1)
C13	0.051 (1)	0.053 (2)	0.055 (2)	0.008 (1)	0.003 (1)	−0.004 (1)
C14	0.053 (2)	0.064 (2)	0.080 (2)	−0.003 (1)	0.011 (1)	−0.003 (2)
C15	0.077 (2)	0.057 (2)	0.073 (2)	0.002 (2)	0.023 (2)	0.010 (1)
C16	0.072 (2)	0.053 (2)	0.057 (2)	0.010 (1)	0.013 (1)	0.009 (1)
C17	0.056 (1)	0.044 (1)	0.048 (1)	0.011 (1)	0.005 (1)	0.003 (1)
C18	0.049 (2)	0.088 (2)	0.072 (2)	0.010 (1)	−0.013 (1)	−0.002 (2)
C19	0.044 (1)	0.047 (1)	0.043 (1)	0.011 (1)	0.001 (1)	0.006 (1)
C20	0.064 (2)	0.049 (2)	0.057 (2)	0.010 (1)	0.012 (1)	0.002 (1)
C21	0.085 (2)	0.063 (2)	0.067 (2)	0.011 (2)	0.017 (2)	−0.015 (2)
C22	0.074 (2)	0.093 (2)	0.050 (2)	0.018 (2)	0.010 (1)	−0.007 (2)
C23	0.086 (2)	0.084 (2)	0.056 (2)	0.019 (2)	0.019 (2)	0.015 (2)
C24	0.080 (2)	0.056 (2)	0.056 (2)	0.014 (1)	0.012 (1)	0.008 (1)
C25	0.050 (1)	0.042 (1)	0.048 (1)	0.017 (1)	−0.005 (1)	−0.003 (1)
C26	0.063 (2)	0.043 (1)	0.057 (2)	0.014 (1)	0.001 (1)	0.005 (1)
C27	0.074 (2)	0.049 (2)	0.071 (2)	0.008 (1)	−0.007 (2)	0.007 (1)
C28	0.092 (2)	0.047 (2)	0.093 (2)	0.018 (2)	−0.015 (2)	0.011 (2)
C29	0.107 (3)	0.053 (2)	0.116 (3)	0.042 (2)	0.002 (2)	0.001 (2)
C30	0.081 (2)	0.058 (2)	0.084 (2)	0.036 (2)	0.010 (2)	−0.001 (2)

Geometric parameters (Å, º)

C1—C2	1.564 (3)	C14—H12	0.96
C1—C8	1.529 (4)	C15—C16	1.372 (5)
C1—C12	1.543 (4)	C15—H13	0.96
C1—C19	1.548 (3)	C16—C17	1.380 (4)
C2—C3	1.562 (4)	C16—H14	0.96
C2—H1	0.96	C17—H15	0.96
C2—H2	0.96	C18—H16	0.96
C3—C9	1.522 (3)	C18—H17	0.96
C3—C10	1.536 (4)	C18—H18	0.96
C3—C25	1.525 (4)	C19—C20	1.381 (4)
C4—C5	1.391 (3)	C19—C24	1.388 (4)
C4—C9	1.402 (4)	C20—C21	1.392 (4)
C4—C11	1.510 (4)	C20—H19	0.96
C5—C6	1.383 (4)	C21—C22	1.361 (5)
C5—H3	0.96	C21—H20	0.96
C6—C7	1.383 (4)	C22—C23	1.366 (6)
C6—H4	0.96	C22—H21	0.96
C7—C8	1.389 (3)	C23—C24	1.381 (4)
C7—H5	0.96	C23—H22	0.96
C8—C9	1.387 (3)	C24—H23	0.96
C10—H6	0.96	C25—C26	1.389 (4)
C10—H7	0.96	C25—C30	1.387 (4)
C10—H8	0.96	C26—C27	1.382 (4)
C11—H9	0.96	C26—H24	0.96
C11—H10	0.96	C27—C28	1.370 (4)
C11—H11	0.96	C27—H25	0.96
C12—C13	1.404 (4)	C28—C29	1.364 (6)
C12—C17	1.395 (3)	C28—H26	0.96
C13—C14	1.392 (4)	C29—C30	1.391 (5)
C13—C18	1.520 (4)	C29—H27	0.96
C14—C15	1.380 (4)	C30—H28	0.96
C12—C1—C2	110.2 (2)	H12—C14—C13	118.9
C8—C1—C2	100.7 (2)	C15—C14—C13	122.5 (3)
C8—C1—C12	112.2 (2)	C15—C14—H12	118.7
C19—C1—C2	113.0 (2)	C16—C15—H13	120.4
C19—C1—C12	111.7 (2)	C14—C15—H13	120.5
C19—C1—C8	108.5 (2)	C14—C15—C16	119.1 (3)
H2—C2—C1	109.8	C17—C16—C15	119.2 (3)
H1—C2—C1	109.8	H14—C16—C15	120.4
H1—C2—H2	109.5	H14—C16—C17	120.3
C3—C2—C1	108.0 (2)	H15—C17—C16	118.5
C3—C2—H2	109.9	C12—C17—C16	122.9 (3)
C3—C2—H1	109.8	C12—C17—H15	118.6
C2—C3—C9	101.8 (2)	H17—C18—C13	109.3
C25—C3—C9	112.6 (2)	H18—C18—C13	109.5
C25—C3—C2	109.3 (2)	H18—C18—H17	109.5
C10—C3—C9	109.1 (2)	H16—C18—C13	109.6
C10—C3—C2	109.8 (2)	H16—C18—H17	109.5
C10—C3—C25	113.5 (2)	H16—C18—H18	109.5
C5—C4—C9	117.5 (2)	C1—C19—C20	122.0 (2)
C11—C4—C9	123.1 (2)	C24—C19—C20	117.4 (2)
C11—C4—C5	119.4 (3)	C24—C19—C1	120.4 (2)
H3—C5—C4	119.1	C21—C20—H19	119.6
C6—C5—C4	121.8 (3)	C19—C20—H19	119.4
C6—C5—H3	119.1	C19—C20—C21	121.0 (3)
C5—C6—C7	120.3 (2)	C20—C21—H20	119.7
H4—C6—C7	119.9	C22—C21—H20	119.8
H4—C6—C5	119.9	C22—C21—C20	120.5 (3)
C8—C7—C6	118.9 (2)	C21—C22—H21	120.4
H5—C7—C6	120.5	C23—C22—H21	120.2
H5—C7—C8	120.6	C23—C22—C21	119.4 (3)
C9—C8—C1	112.6 (2)	H22—C23—C22	119.8
C7—C8—C1	126.6 (2)	C24—C23—C22	120.5 (3)
C7—C8—C9	120.8 (2)	C24—C23—H22	119.6
C3—C9—C4	127.9 (2)	C19—C24—H23	119.4
C8—C9—C4	120.7 (2)	C23—C24—H23	119.5
C8—C9—C3	111.4 (2)	C23—C24—C19	121.1 (3)
H6—C10—H7	109.5	C3—C25—C26	119.6 (2)
H8—C10—H7	109.5	C30—C25—C26	117.2 (2)
H8—C10—H6	109.5	C30—C25—C3	123.2 (2)
C3—C10—H7	109.4	H24—C26—C25	119.0
C3—C10—H6	109.5	C27—C26—C25	121.9 (2)
C3—C10—H8	109.4	C27—C26—H24	119.1
H10—C11—H11	109.5	C26—C27—H25	120.0
C4—C11—H11	109.5	C28—C27—H25	120.0
C4—C11—H10	109.4	C28—C27—C26	120.0 (3)
H9—C11—H11	109.5	C27—C28—H26	120.3
H9—C11—H10	109.5	C29—C28—H26	120.5
H9—C11—C4	109.6	C29—C28—C27	119.2 (3)
C17—C12—C1	120.3 (2)	H27—C29—C30	119.5
C13—C12—C1	122.1 (2)	C28—C29—C30	121.2 (3)
C13—C12—C17	117.5 (2)	C28—C29—H27	119.3
C12—C13—C18	123.7 (3)	H28—C30—C29	119.8
C14—C13—C18	117.5 (3)	C25—C30—C29	120.5 (3)
C14—C13—C12	118.7 (2)	C25—C30—H28	119.8