1,3,5-Tris­(phenyl­thio­methyl)-2,4,6-tri­methyl­benzene

The molecular structure of the title compound, C₃₀H₃₀S₃, adopts a cis, trans, trans-conformation for the three phenyl­thio groups about the central benzyl ring, which is analogous to a `soft-shelled crawling turtle'. The dihedral angle between the `head' phenyl ring and the central phenyl ring is 89.0 (4)°, while the angles between the two `foot' phenyl rings and the central ring are 18.0 (6) and 6.7 (4)°, respectively.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.054
• wR factor = 0.160
• Data-to-parameter ratio = 15.8

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry

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S1. Comment

Crystal engineering and supramolecular chemistry aimed at developing systems to perform optical, magnetic and electronic functions as well as intercalation systems for ion- or molecule-exchange and catalytic properties are some of the most attractive research areas in present years, and much progress has been achieved in both theoretical studies and their applications as new materials (Yuge et al. 1996). One of the most remarkable developments in crystal engineering may be the possibility to select suitable building blocks to assemble into structures with specific topologies (Goodgame et al., 1993; Gormley et al., 2000). Multithioether ligands possess unusual potential for structure control in inorganic chemistry, and a lot of unusual crystal structures of complexes with multithioether ligands (Bu et al., 2002; Alcock et al., 1978) have been reported. There are, however, just a few examples of organic ligands of multithioether whose crystals have been structurally characterized (Gormley et al., 2000). In recent years, one of our interests has been to further study the complexing abilities and the reactivities of a few types of dipodal or tripodal flexible ligands including disulfoxide, trisulfoxide, dithioether, trithioether, and their derivatives. As part of our structural studies of the trithioether series, we report here the synthesis and structure of a new flexible tripodal ligand, 1,3,5-tris(phenylthiomethyl)-2,4,6-trimethylbenzene, (I); more work on the reaction with transition metal ions is still in progress.

The title molecule has a cis, trans, trans-conformation (Fig. 1) for the three phenylthio groups about the central phenyl ring, which is analogous to a `soft-shelled crawling turtle'. The phenylthio 1 (composed of S1 and C21—C26) and 2 (composed of S2 and C31—C36) are on the same side of the central phenyl ring, when viewed together with the two adjacent methyl groups (C11 and C12), would consist of the four feet of this `soft-shelled turtle'. While phenlythio 3 (S3, C41—C46) is on the other side of the phenyl ring, which forms the head held high. The remaining methyl group (C10) would be the tail. The dihedral angle between the head phenyl ring (phenyl 3) and the central phenyl ring is 89.0 (4)°, while the angles between the other two phenyl rings (phenyl 1 and 2) and the central phenyl ring are 18.0 (6) and 6.7 (4)°, respectively, and the dihedral angle between the two rear foot phenyl rings (phenyl 1 and 2) is 21.3 (3)°. All the above shows that whole molecule is assuredly like a `soft-shelled crawling turtle'.

S2. Experimental

1,3,5-Tris(bromethyl)-2,4,6-trimethylbenzene was prepared according to a reported procedure and was characterized by NMR and IR analysis, giving results consistent with those in the literature (van der Made et al., 1993). Phenylthio-potassium was obtained by the reaction of KOH with thiophenol in warm EtOH. 1,3,5-Tris(phenylthiomethyl)-2,4,6-trimethylbenzene, (I), was synthesized by the reaction of 1,3,5-tris(bromethyl)-2,4,6-trimethylbenzene and thiophenyl-potassium in EtOH at 353 K; yield: 86%; m.p. 381–383 K; IR (KBr): 2957(w), 2921(w), 1584(m), 1572(m), 1479(s), 1438(s), 1226(m), 1091(m), 1024(m), 755(s), 689(s), 471(w)cm^-1; ¹H NMR (CDCl₃): δ 2.45 (3H, s), 4.19 (2H, s), 7.22–7.40 (5H, m); analysis calculated for C₃₀H₃₀S₃: C 73.00, H 6.21%; found: C 73.12, H 6.18%. Colorless single crystals of (I) were obtained by recrystallization from acetonitrile.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL.

Figures

Fig. 1. View of the title compound with 30% probability ellipsoids.

1,3,5-Tris(phenylthiomethyl)-2,4,6-Trimethylbenzene

Crystal data

C30H30S3	Dx = 1.215 Mg m^−3
Mr = 486.72	Melting point = 381–383 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0660 (6) Å	Cell parameters from 2901 reflections
b = 18.5382 (13) Å	θ = 1.7–25.1°
c = 15.9779 (11) Å	µ = 0.30 mm^−1
β = 97.785 (2)°	T = 293 K
V = 2660.6 (3) Å^3	Prism, colorless
Z = 4	0.30 × 0.25 × 0.20 mm
F(000) = 1032

Data collection

Siemens SMART CCD diffractometer	4703 independent reflections
Radiation source: fine-focus sealed tube	2679 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 25.1°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −10→4
Tmin = 0.917, Tmax = 0.943	k = −18→22
9493 measured reflections	l = −18→19

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.070P)^2 + 0.7755P] where P = (Fo^2 + 2Fc^2)/3
4703 reflections	(Δ/σ)max = 0.005
298 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.24 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
S1	0.15919 (4)	−0.23065 (2)	0.56165 (3)	0.08914 (13)
S2	0.36132 (4)	0.07225 (2)	0.70997 (2)	0.08036 (14)
S3	0.12226 (4)	0.05360 (2)	0.27816 (2)	0.06640 (11)
C1	0.35191 (12)	−0.06840 (7)	0.55858 (8)	0.0548 (4)
C2	0.34001 (12)	0.00731 (7)	0.55435 (7)	0.0528 (4)
C3	0.23419 (11)	0.03940 (7)	0.49402 (7)	0.0508 (4)
C4	0.14680 (11)	−0.00334 (7)	0.43446 (7)	0.0511 (4)
C5	0.16710 (12)	−0.07840 (7)	0.43336 (7)	0.0525 (4)
C6	0.26918 (12)	−0.11043 (7)	0.49651 (7)	0.0539 (4)
C7	0.44373 (13)	0.05267 (8)	0.61383 (8)	0.0646 (4)
H7A	0.4641	0.0975	0.5863	0.078*
H7B	0.5373	0.0273	0.6286	0.078*
C8	0.03248 (13)	0.03171 (7)	0.36965 (8)	0.0587 (4)
H8A	−0.0058	0.0752	0.3928	0.070*
H8B	−0.0501	−0.0010	0.3538	0.070*
C9	0.29055 (14)	−0.19118 (7)	0.49792 (9)	0.0671 (4)
H9A	0.3917	−0.2030	0.5219	0.081*
H9B	0.2730	−0.2102	0.4409	0.081*
C10	0.45595 (14)	−0.10300 (9)	0.62991 (9)	0.0768 (5)
H10A	0.4516	−0.1545	0.6240	0.115*
H10B	0.4261	−0.0895	0.6831	0.115*
H10C	0.5559	−0.0868	0.6276	0.115*
C11	0.21394 (15)	0.12047 (7)	0.49345 (9)	0.0722 (5)
H11A	0.2820	0.1415	0.5381	0.108*
H11B	0.1137	0.1318	0.5018	0.108*
H11C	0.2333	0.1395	0.4401	0.108*
C12	0.08374 (16)	−0.12424 (8)	0.36393 (9)	0.0754 (5)
H12A	0.0190	−0.0941	0.3264	0.113*
H12B	0.0257	−0.1598	0.3884	0.113*
H12C	0.1537	−0.1478	0.3330	0.113*
C21	0.20225 (13)	−0.32271 (7)	0.55613 (9)	0.0635 (4)
C22	0.12771 (17)	−0.36647 (9)	0.49694 (11)	0.0928 (6)
H22A	0.0544	−0.3473	0.4567	0.111*
C23	0.1603 (2)	−0.44050 (10)	0.49580 (13)	0.1260 (8)
H23A	0.1088	−0.4707	0.4555	0.151*
C24	0.2686 (2)	−0.46698 (10)	0.55464 (14)	0.1406 (8)
H24A	0.2917	−0.5159	0.5542	0.169*
C25	0.3420 (2)	−0.42476 (10)	0.61247 (13)	0.1273 (8)
H25A	0.4163	−0.4441	0.6519	0.153*
C26	0.30949 (17)	−0.35287 (8)	0.61478 (10)	0.0876 (6)
H26A	0.3606	−0.3240	0.6566	0.105*
C31	0.51273 (14)	0.11943 (8)	0.76665 (8)	0.0618 (4)
C32	0.62236 (18)	0.08291 (8)	0.81641 (10)	0.0853 (6)
H32A	0.6166	0.0330	0.8211	0.102*
C33	0.74132 (19)	0.11922 (10)	0.85977 (11)	0.1020 (7)
H33A	0.8148	0.0939	0.8940	0.122*
C34	0.75159 (18)	0.19187 (9)	0.85262 (10)	0.0907 (6)
H34A	0.8319	0.2164	0.8820	0.109*
C35	0.6458 (2)	0.22828 (9)	0.80313 (11)	0.1030 (7)
H35A	0.6539	0.2780	0.7976	0.124*
C36	0.52593 (18)	0.19278 (8)	0.76052 (11)	0.0914 (6)
H36A	0.4526	0.2188	0.7270	0.110*
C41	−0.01243 (13)	0.10182 (7)	0.21093 (8)	0.0547 (4)
C42	−0.15459 (14)	0.11605 (8)	0.22726 (8)	0.0666 (5)
H42A	−0.1860	0.0992	0.2767	0.080*
C43	−0.25084 (17)	0.15537 (9)	0.17031 (10)	0.0836 (6)
H43A	−0.3463	0.1654	0.1823	0.100*
C44	−0.20824 (17)	0.17988 (9)	0.09651 (10)	0.0882 (6)
H44A	−0.2742	0.2059	0.0582	0.106*
C45	−0.06792 (17)	0.16561 (9)	0.08004 (10)	0.0916 (6)
H45A	−0.0377	0.1822	0.0301	0.110*
C46	0.02969 (16)	0.12702 (8)	0.13608 (8)	0.0750 (5)
H46A	0.1252	0.1177	0.1237	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0997 (2)	0.0550 (2)	0.1249 (3)	0.01650 (19)	0.05909 (19)	0.0168 (2)
S2	0.06341 (19)	0.1145 (3)	0.0660 (2)	−0.0135 (2)	0.01883 (16)	−0.0179 (2)
S3	0.05939 (17)	0.0787 (2)	0.0636 (2)	0.00774 (17)	0.01724 (15)	0.00884 (18)
C1	0.0435 (6)	0.0702 (8)	0.0518 (7)	0.0075 (6)	0.0104 (5)	0.0045 (6)
C2	0.0449 (6)	0.0621 (8)	0.0533 (7)	−0.0004 (6)	0.0132 (5)	−0.0015 (6)
C3	0.0466 (6)	0.0516 (7)	0.0564 (7)	0.0007 (5)	0.0149 (5)	0.0015 (6)
C4	0.0462 (6)	0.0556 (7)	0.0536 (7)	0.0024 (6)	0.0145 (5)	0.0040 (6)
C5	0.0520 (6)	0.0538 (7)	0.0543 (7)	−0.0032 (6)	0.0163 (5)	−0.0001 (6)
C6	0.0524 (6)	0.0519 (7)	0.0603 (7)	0.0074 (6)	0.0181 (6)	0.0072 (6)
C7	0.0560 (6)	0.0803 (9)	0.0600 (7)	−0.0066 (7)	0.0171 (6)	−0.0047 (7)
C8	0.0525 (6)	0.0683 (8)	0.0572 (7)	0.0060 (6)	0.0142 (6)	0.0075 (7)
C9	0.0666 (7)	0.0592 (8)	0.0801 (9)	0.0096 (7)	0.0268 (6)	0.0056 (7)
C10	0.0585 (7)	0.0961 (11)	0.0755 (9)	0.0162 (8)	0.0083 (7)	0.0148 (8)
C11	0.0832 (8)	0.0573 (8)	0.0778 (9)	0.0040 (7)	0.0167 (7)	−0.0011 (7)
C12	0.0836 (9)	0.0617 (9)	0.0801 (10)	−0.0067 (8)	0.0085 (8)	−0.0031 (8)
C21	0.0594 (7)	0.0549 (8)	0.0797 (8)	0.0037 (6)	0.0223 (6)	0.0106 (7)
C22	0.0823 (9)	0.0896 (11)	0.1058 (12)	0.0003 (9)	0.0102 (9)	−0.0048 (10)
C23	0.1511 (15)	0.0986 (13)	0.1350 (15)	−0.0440 (12)	0.0438 (12)	−0.0372 (11)
C24	0.1936 (17)	0.0644 (11)	0.1824 (18)	0.0109 (12)	0.0930 (13)	0.0147 (12)
C25	0.1349 (13)	0.1054 (12)	0.1500 (15)	0.0572 (11)	0.0491 (12)	0.0591 (11)
C26	0.0872 (10)	0.0807 (10)	0.0935 (11)	0.0094 (9)	0.0075 (9)	0.0186 (9)
C31	0.0604 (7)	0.0750 (9)	0.0498 (7)	0.0062 (7)	0.0070 (6)	−0.0084 (7)
C32	0.1030 (11)	0.0635 (9)	0.0829 (10)	0.0051 (9)	−0.0104 (9)	0.0014 (8)
C33	0.1044 (11)	0.0963 (12)	0.0924 (12)	0.0162 (10)	−0.0335 (10)	0.0000 (10)
C34	0.0974 (10)	0.0911 (11)	0.0753 (10)	−0.0082 (9)	−0.0186 (9)	−0.0156 (9)
C35	0.1286 (13)	0.0634 (10)	0.1048 (13)	−0.0023 (10)	−0.0282 (11)	−0.0080 (9)
C36	0.0999 (10)	0.0647 (9)	0.0998 (12)	0.0176 (9)	−0.0222 (10)	0.0044 (9)
C41	0.0648 (7)	0.0501 (7)	0.0486 (7)	−0.0102 (6)	0.0052 (6)	−0.0049 (6)
C42	0.0681 (8)	0.0751 (9)	0.0559 (8)	0.0050 (7)	0.0057 (6)	0.0086 (7)
C43	0.0717 (8)	0.0963 (11)	0.0796 (10)	0.0061 (8)	−0.0014 (8)	0.0087 (9)
C44	0.0992 (10)	0.0791 (10)	0.0772 (10)	−0.0163 (9)	−0.0210 (9)	0.0177 (9)
C45	0.1034 (10)	0.1036 (11)	0.0637 (9)	−0.0422 (9)	−0.0031 (8)	0.0221 (8)
C46	0.0790 (8)	0.0906 (10)	0.0560 (8)	−0.0192 (8)	0.0112 (7)	0.0058 (8)

Geometric parameters (Å, º)

S1—C21	1.7556 (14)	C21—C22	1.355 (2)
S1—C9	1.8219 (14)	C21—C26	1.3745 (19)
S2—C31	1.7699 (13)	C22—C23	1.405 (2)
S2—C7	1.8331 (14)	C22—H22A	0.9300
S3—C41	1.7575 (12)	C23—C24	1.356 (3)
S3—C8	1.8128 (13)	C23—H23A	0.9300
C1—C6	1.3971 (16)	C24—C25	1.320 (3)
C1—C2	1.4086 (18)	C24—H24A	0.9300
C1—C10	1.5196 (17)	C25—C26	1.366 (2)
C2—C3	1.3974 (15)	C25—H25A	0.9300
C2—C7	1.5008 (17)	C26—H26A	0.9300
C3—C4	1.3989 (16)	C31—C32	1.3654 (19)
C3—C11	1.5139 (18)	C31—C36	1.370 (2)
C4—C5	1.4041 (17)	C32—C33	1.376 (2)
C4—C8	1.5093 (16)	C32—H32A	0.9300
C5—C6	1.4050 (16)	C33—C34	1.356 (2)
C5—C12	1.5155 (18)	C33—H33A	0.9300
C6—C9	1.5091 (18)	C34—C35	1.340 (2)
C7—H7A	0.9700	C34—H34A	0.9300
C7—H7B	0.9700	C35—C36	1.370 (2)
C8—H8A	0.9700	C35—H35A	0.9300
C8—H8B	0.9700	C36—H36A	0.9300
C9—H9A	0.9700	C41—C42	1.3747 (18)
C9—H9B	0.9700	C41—C46	1.3849 (19)
C10—H10A	0.9600	C42—C43	1.3805 (19)
C10—H10B	0.9600	C42—H42A	0.9300
C10—H10C	0.9600	C43—C44	1.367 (2)
C11—H11A	0.9600	C43—H43A	0.9300
C11—H11B	0.9600	C44—C45	1.360 (2)
C11—H11C	0.9600	C44—H44A	0.9300
C12—H12A	0.9600	C45—C46	1.372 (2)
C12—H12B	0.9600	C45—H45A	0.9300
C12—H12C	0.9600	C46—H46A	0.9300
C21—S1—C9	101.29 (6)	H12B—C12—H12C	109.5
C31—S2—C7	98.67 (6)	C22—C21—C26	118.17 (13)
C41—S3—C8	104.84 (6)	C22—C21—S1	121.59 (11)
C6—C1—C2	119.43 (10)	C26—C21—S1	120.18 (11)
C6—C1—C10	121.06 (12)	C21—C22—C23	120.54 (15)
C2—C1—C10	119.50 (11)	C21—C22—H22A	119.7
C3—C2—C1	119.89 (10)	C23—C22—H22A	119.7
C3—C2—C7	120.73 (11)	C24—C23—C22	118.60 (18)
C1—C2—C7	119.37 (10)	C24—C23—H23A	120.7
C2—C3—C4	120.05 (11)	C22—C23—H23A	120.7
C2—C3—C11	119.88 (10)	C25—C24—C23	121.29 (18)
C4—C3—C11	120.07 (10)	C25—C24—H24A	119.4
C3—C4—C5	120.45 (10)	C23—C24—H24A	119.4
C3—C4—C8	119.73 (11)	C24—C25—C26	120.49 (18)
C5—C4—C8	119.81 (10)	C24—C25—H25A	119.8
C4—C5—C6	118.98 (10)	C26—C25—H25A	119.8
C4—C5—C12	120.77 (10)	C25—C26—C21	120.89 (15)
C6—C5—C12	120.22 (11)	C25—C26—H26A	119.6
C1—C6—C5	120.80 (11)	C21—C26—H26A	119.6
C1—C6—C9	119.15 (10)	C32—C31—C36	118.05 (13)
C5—C6—C9	120.04 (11)	C32—C31—S2	120.39 (11)
C2—C7—S2	110.50 (9)	C36—C31—S2	121.55 (10)
C2—C7—H7A	109.6	C31—C32—C33	120.63 (15)
S2—C7—H7A	109.6	C31—C32—H32A	119.7
C2—C7—H7B	109.6	C33—C32—H32A	119.7
S2—C7—H7B	109.6	C34—C33—C32	120.10 (15)
H7A—C7—H7B	108.1	C34—C33—H33A	119.9
C4—C8—S3	107.94 (8)	C32—C33—H33A	119.9
C4—C8—H8A	110.1	C35—C34—C33	119.89 (15)
S3—C8—H8A	110.1	C35—C34—H34A	120.1
C4—C8—H8B	110.1	C33—C34—H34A	120.1
S3—C8—H8B	110.1	C34—C35—C36	120.49 (16)
H8A—C8—H8B	108.4	C34—C35—H35A	119.8
C6—C9—S1	108.32 (9)	C36—C35—H35A	119.8
C6—C9—H9A	110.0	C31—C36—C35	120.83 (14)
S1—C9—H9A	110.0	C31—C36—H36A	119.6
C6—C9—H9B	110.0	C35—C36—H36A	119.6
S1—C9—H9B	110.0	C42—C41—C46	118.32 (12)
H9A—C9—H9B	108.4	C42—C41—S3	124.97 (10)
C1—C10—H10A	109.5	C46—C41—S3	116.70 (10)
C1—C10—H10B	109.5	C41—C42—C43	120.09 (13)
H10A—C10—H10B	109.5	C41—C42—H42A	120.0
C1—C10—H10C	109.5	C43—C42—H42A	120.0
H10A—C10—H10C	109.5	C44—C43—C42	121.12 (14)
H10B—C10—H10C	109.5	C44—C43—H43A	119.4
C3—C11—H11A	109.5	C42—C43—H43A	119.4
C3—C11—H11B	109.5	C45—C44—C43	118.91 (14)
H11A—C11—H11B	109.5	C45—C44—H44A	120.5
C3—C11—H11C	109.5	C43—C44—H44A	120.5
H11A—C11—H11C	109.5	C44—C45—C46	120.85 (15)
H11B—C11—H11C	109.5	C44—C45—H45A	119.6
C5—C12—H12A	109.5	C46—C45—H45A	119.6
C5—C12—H12B	109.5	C45—C46—C41	120.71 (14)
H12A—C12—H12B	109.5	C45—C46—H46A	119.6
C5—C12—H12C	109.5	C41—C46—H46A	119.6
H12A—C12—H12C	109.5