supplementary materials


bt6973 scheme

Acta Cryst. (2014). E70, o539    [ doi:10.1107/S1600536814007594 ]

{[2-Methyl-2-(phen­oxy­meth­yl)propane-1,3-di­yl]bis­(­oxy)}di­benzene

Z. Moussa, H. T. Al-Masri, A. Shraim and M. Fettouhi

CCDC reference: 942596

Abstract top

The title compound, C23H24O3, was obtained in a one-step (60% yield) synthesis from 1,1,1-tris(hydroxymethyl)ethane. It features a tripodal ligand capable of complexing metal centres. One of the three conformations involving the methyl group, the central C-C bond and the phenoxy substituents is antiperiplanar while the two others are synclinal [the corresponding C-C-C-O torsion angles are -174.6 (1), -53.2 (2) and -47.3 (2)°]. In the crystal, C-H...O inter­actions link the molecules into [010] chains.

Comment top

α,α,α-tris(hydroxymethyl)ethane has been widely used in the design of polypodal ligands (Viguier et al., 2001; Alajarín et al., 2007; Beaufort et al., 2007) capable of forming stable complexes with transition metals [Cu(I), Cu(II), Ni(II), Pd(II), Y(III)] and a variety of lanthanide(III) cations (La3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+). The main step in the preparation of such compounds involves nucleophilic displacement of the hydroxyl group with various nucleophiles. The hydroxyl group is initially converted to a tosylate (Beaufort et al., 2007) or a halogen (Alajarín et al., 2007) before the substitution step is carried out. The title compound provides a related tripodal ligand that can be readily synthesized in a single step and in good yield. In the course of investigating its use as a tripodal ligand in transition metal complexation reactions, we examined its structure to determine the preferred conformation, identify the principal intermolecular interactions, and extract detailed geometric information.

Initial attempts to prepare the title compound by reacting phenol or sodium phenoxide with α,α,α-tris[(4-tolylsulfonyl)methyl]ethane or α,α,α-tris(chloromethyl)ethane were unsuccessful due to the poor nucleophilic character of phenol and its alkali metal salts. However, converting α,α,α-tris(hydroxymethyl)ethane to the corresponding trifluoromethanesulfonate derivative gave a more effective substrate with a much superior leaving group ability. Thus, the latter derivative reacted with sodium phenoxide under very mild conditions to afford the title compound in 60% isolated yield.

The X-ray structure determination of the tripodal O,O,O-ligand shows the central C2-atom to be bonded to a methyl groups and three phenoxymethyl groups. The geometry around the central C-atom could be described as a slightly distorted tetrahedron because the bond angles deviate from the ideal value of 109.47°. The C(3)-C(2)-C(10) [111.04 (13)°] and C(1)-C(2)-C(17) [110.26 (13)°], and C(1)-C(2)-C(10) [111.15 (13)°] angles are wide, and the other three angles are narrow. The three phenoxymethyl arms are tilted away from the C-center due to steric interactions. One of the three conformations involving the methyl group, the central C—C bond and each one of the three phenoxy substituents is antiperiplanar while the two others are synclinal. The corresponding torsion angles are C1—C2—C3—O1: -174.6 (1)°, C1—C2—C17—O3: -53.2 (2)° and C1—C2—C10—O2: -47.3 (2)° respectively. The bond angles and bond distances are in good agreement with those reported for the only one reported analog namely 1,3-diphenoxy-2,2-bis(phenoxymethyl)propane (Laliberté et al., 2003).

The only remarkable short intermolecular contact is a C-H···O interaction.

Related literature top

For details of the synthesis, see: Viguier et al. (2001); Alajarín et al. (2007); Beaufort et al. (2007). For a related structure, see: Laliberté et al. (2003).

Experimental top

Preparation of (2-methyl-2-(phenoxymethyl)propane-1,3-diyl)bis(oxy)dibenzene

1,1,1-tris(hydroxymethyl)ethane (600 mg, 5 mmol) was dissolved in pyridine (10 ml) and cooled to 273K in an ice/water bath. The colorless solution was treated dropwise over ten minutes with trifluoromethanesulfonic anhydride (4.34 g, 2.6 ml, 15.4 mmol) to give a deep dark red homogeneous solution and stirring was continued for another 50 minutes. Simultaneously and in a separate flask, NaH (1.98 g, 60%, 50 mmol) was washed with hexanes and suspended in THF (30 ml) at 273K. Phenol (4.23 g, 45 mmol) was added in portions to the stirred suspension over 1 h. The trifluoromethanesulfonate solution was then slowly added to the sodium phenoxide solution at 273K to give a light reddish yellow color. The ice bath was removed and the mixture was subsequently stirred overnight at room temperature. The mixture was diluted with diethyl ether (50 ml) and the ether layer was washed with 5% HCl solution (3 x 20 ml), 1 N solution of NaOH (3 x 20 ml), saturated NaCl solution (3 x 20 ml), dried (Na2SO4) and concentrated in vacuo. 1H NMR analysis of the crude indicated that it consisted of a 2:1 mixture of the product and corresponding disubstituted analogue. The residue was initially chromatographed (elution with 90% hexanes-ethyl acetate) to provide an unseparated mixture of the aforementioned products. Further chromatographic separation with hexanes and re-crystallization (hexanes) afforded 1.04 g (60%) of the tripodal ligand as a colorless crystalline solid: 1H NMR (CDCl3, 400 MHz) δ 7.30–7.20 (m, 6H, Ar—H), 6.97–6.88 (m, 9H, Ar—H), 4.09 (s, 6H, OCH2), 1.33 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz) δ 159.1 (C), 129.4 (CH), 120.8 (CH), 114.6 (CH), 70.0 (CH2), 40.4 (C), 17.3 (CH3).

Refinement top

All the H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radius.
(I) top
Crystal data top
C23H24O3F(000) = 744
Mr = 348.42Dx = 1.205 Mg m3
Monoclinic, P21/nMelting point: 340 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 13.5755 (15) ÅCell parameters from 16758 reflections
b = 6.2829 (7) Åθ = 1.7–28.3°
c = 22.514 (3) ŵ = 0.08 mm1
β = 91.033 (2)°T = 295 K
V = 1920.0 (4) Å3Block, colourless
Z = 40.41 × 0.32 × 0.11 mm
Data collection top
Bruker SMART APEX area-detector
diffractometer
4770 independent reflections
Radiation source: normal-focus sealed tube2614 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
ω scansθmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1818
Tmin = 0.969, Tmax = 0.991k = 88
16758 measured reflectionsl = 2629
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0497P)2 + 0.108P]
where P = (Fo2 + 2Fc2)/3
4770 reflections(Δ/σ)max < 0.001
236 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C23H24O3V = 1920.0 (4) Å3
Mr = 348.42Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.5755 (15) ŵ = 0.08 mm1
b = 6.2829 (7) ÅT = 295 K
c = 22.514 (3) Å0.41 × 0.32 × 0.11 mm
β = 91.033 (2)°
Data collection top
Bruker SMART APEX area-detector
diffractometer
4770 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2614 reflections with I > 2σ(I)
Tmin = 0.969, Tmax = 0.991Rint = 0.045
16758 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.16 e Å3
S = 1.00Δρmin = 0.14 e Å3
4770 reflectionsAbsolute structure: ?
236 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.68030 (8)0.63321 (17)0.10973 (5)0.0513 (3)
O20.82639 (8)0.16266 (19)0.06970 (5)0.0576 (3)
O30.68819 (9)0.4660 (2)0.06922 (5)0.0603 (3)
C10.64308 (13)0.1538 (3)0.01456 (8)0.0575 (5)
H1A0.67500.10200.02030.086*
H1B0.57420.17380.00600.086*
H1C0.65120.05240.04620.086*
C20.68907 (11)0.3661 (2)0.03331 (7)0.0431 (4)
C30.64647 (12)0.4268 (3)0.09311 (7)0.0469 (4)
H3A0.57510.42600.09040.056*
H3B0.66690.32390.12300.056*
C40.65081 (11)0.7116 (3)0.16385 (6)0.0423 (4)
C50.69030 (11)0.9064 (3)0.17973 (7)0.0470 (4)
H50.73270.97620.15430.056*
C60.66682 (13)0.9972 (3)0.23330 (7)0.0564 (5)
H60.69271.12930.24370.068*
C70.60515 (14)0.8929 (3)0.27141 (8)0.0643 (5)
H70.59050.95260.30800.077*
C80.56545 (14)0.7011 (3)0.25532 (8)0.0627 (5)
H80.52310.63220.28100.075*
C90.58723 (12)0.6073 (3)0.20120 (7)0.0524 (4)
H90.55960.47730.19040.063*
C100.80135 (11)0.3501 (3)0.03726 (7)0.0470 (4)
H10A0.82840.34320.00230.056*
H10B0.82840.47440.05730.056*
C110.92434 (11)0.1140 (3)0.07759 (7)0.0484 (4)
C120.94461 (14)0.0863 (3)0.10011 (8)0.0616 (5)
H120.89350.18020.10790.074*
C131.04092 (15)0.1463 (4)0.11106 (9)0.0717 (6)
H131.05450.28150.12590.086*
C141.11664 (15)0.0090 (4)0.10026 (9)0.0795 (6)
H141.18150.04970.10790.095*
C151.09607 (14)0.1878 (4)0.07819 (10)0.0836 (7)
H151.14750.28140.07100.100*
C161.00011 (13)0.2518 (3)0.06624 (8)0.0655 (5)
H160.98720.38630.05070.079*
C170.66205 (12)0.5391 (3)0.01163 (7)0.0498 (4)
H17A0.59190.56820.01060.060*
H17B0.69730.66930.00210.060*
C180.66232 (11)0.5878 (3)0.11761 (7)0.0494 (4)
C190.68929 (13)0.5068 (3)0.17178 (8)0.0652 (5)
H190.72270.37780.17370.078*
C200.66669 (15)0.6174 (4)0.22296 (9)0.0786 (6)
H200.68470.56210.25950.094*
C210.61777 (15)0.8086 (4)0.22066 (9)0.0769 (6)
H210.60300.88310.25540.092*
C220.59107 (13)0.8883 (3)0.16677 (9)0.0664 (5)
H220.55771.01740.16510.080*
C230.61290 (12)0.7797 (3)0.11474 (8)0.0543 (5)
H230.59460.83520.07830.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0664 (7)0.0418 (7)0.0462 (6)0.0108 (6)0.0132 (5)0.0045 (5)
O20.0462 (6)0.0552 (8)0.0716 (8)0.0021 (5)0.0038 (5)0.0187 (6)
O30.0792 (8)0.0587 (8)0.0431 (6)0.0172 (6)0.0000 (6)0.0039 (6)
C10.0607 (10)0.0499 (11)0.0618 (11)0.0042 (9)0.0006 (8)0.0106 (9)
C20.0465 (9)0.0377 (9)0.0450 (9)0.0000 (7)0.0016 (7)0.0034 (7)
C30.0514 (9)0.0395 (10)0.0500 (10)0.0053 (7)0.0047 (7)0.0030 (7)
C40.0476 (9)0.0421 (10)0.0371 (8)0.0025 (7)0.0002 (7)0.0013 (7)
C50.0520 (9)0.0431 (10)0.0459 (9)0.0017 (8)0.0006 (7)0.0026 (8)
C60.0676 (11)0.0482 (11)0.0531 (10)0.0021 (9)0.0083 (9)0.0066 (9)
C70.0793 (13)0.0702 (14)0.0435 (10)0.0072 (11)0.0027 (9)0.0106 (10)
C80.0680 (11)0.0719 (15)0.0488 (10)0.0004 (10)0.0141 (9)0.0055 (10)
C90.0585 (10)0.0504 (11)0.0484 (10)0.0070 (8)0.0057 (8)0.0010 (8)
C100.0512 (9)0.0416 (10)0.0483 (9)0.0002 (7)0.0034 (7)0.0037 (8)
C110.0469 (9)0.0559 (12)0.0425 (9)0.0015 (8)0.0022 (7)0.0006 (8)
C120.0627 (11)0.0554 (12)0.0666 (12)0.0047 (9)0.0001 (9)0.0038 (10)
C130.0754 (14)0.0700 (15)0.0696 (13)0.0224 (12)0.0040 (10)0.0024 (11)
C140.0534 (12)0.110 (2)0.0745 (14)0.0163 (12)0.0008 (10)0.0097 (14)
C150.0505 (12)0.108 (2)0.0927 (16)0.0062 (12)0.0015 (10)0.0268 (14)
C160.0534 (11)0.0731 (14)0.0701 (12)0.0013 (10)0.0019 (9)0.0184 (11)
C170.0528 (9)0.0512 (11)0.0453 (9)0.0064 (8)0.0006 (7)0.0051 (8)
C180.0448 (9)0.0575 (12)0.0456 (9)0.0024 (8)0.0038 (7)0.0010 (8)
C190.0677 (12)0.0767 (15)0.0513 (11)0.0111 (10)0.0068 (9)0.0016 (10)
C200.0789 (14)0.109 (2)0.0487 (11)0.0070 (13)0.0101 (10)0.0062 (12)
C210.0679 (13)0.1007 (19)0.0622 (13)0.0049 (12)0.0022 (10)0.0246 (12)
C220.0604 (11)0.0630 (13)0.0757 (14)0.0007 (10)0.0049 (10)0.0130 (11)
C230.0544 (10)0.0543 (12)0.0539 (10)0.0033 (9)0.0044 (8)0.0009 (9)
Geometric parameters (Å, º) top
O1—C41.3804 (17)C10—H10A0.9700
O1—C31.4238 (18)C10—H10B0.9700
O2—C111.3729 (19)C11—C161.372 (2)
O2—C101.4240 (18)C11—C121.382 (2)
O3—C181.3718 (19)C12—C131.379 (3)
O3—C171.4263 (18)C12—H120.9300
C1—C21.529 (2)C13—C141.368 (3)
C1—H1A0.9600C13—H130.9300
C1—H1B0.9600C14—C151.359 (3)
C1—H1C0.9600C14—H140.9300
C2—C31.523 (2)C15—C161.385 (3)
C2—C171.525 (2)C15—H150.9300
C2—C101.529 (2)C16—H160.9300
C3—H3A0.9700C17—H17A0.9700
C3—H3B0.9700C17—H17B0.9700
C4—C51.380 (2)C18—C191.377 (2)
C4—C91.381 (2)C18—C231.382 (2)
C5—C61.377 (2)C19—C201.375 (3)
C5—H50.9300C19—H190.9300
C6—C71.376 (2)C20—C211.374 (3)
C6—H60.9300C20—H200.9300
C7—C81.366 (3)C21—C221.367 (3)
C7—H70.9300C21—H210.9300
C8—C91.390 (2)C22—C231.383 (2)
C8—H80.9300C22—H220.9300
C9—H90.9300C23—H230.9300
C4—O1—C3117.37 (11)H10A—C10—H10B108.4
C11—O2—C10118.19 (12)C16—C11—O2124.26 (16)
C18—O3—C17118.56 (13)C16—C11—C12119.85 (16)
C2—C1—H1A109.5O2—C11—C12115.86 (15)
C2—C1—H1B109.5C13—C12—C11119.77 (18)
H1A—C1—H1B109.5C13—C12—H12120.1
C2—C1—H1C109.5C11—C12—H12120.1
H1A—C1—H1C109.5C14—C13—C12120.6 (2)
H1B—C1—H1C109.5C14—C13—H13119.7
C3—C2—C17108.50 (13)C12—C13—H13119.7
C3—C2—C1107.62 (13)C15—C14—C13119.26 (19)
C17—C2—C1110.26 (13)C15—C14—H14120.4
C3—C2—C10111.04 (13)C13—C14—H14120.4
C17—C2—C10108.24 (12)C14—C15—C16121.4 (2)
C1—C2—C10111.15 (13)C14—C15—H15119.3
O1—C3—C2109.54 (12)C16—C15—H15119.3
O1—C3—H3A109.8C11—C16—C15119.08 (19)
C2—C3—H3A109.8C11—C16—H16120.5
O1—C3—H3B109.8C15—C16—H16120.5
C2—C3—H3B109.8O3—C17—C2108.23 (13)
H3A—C3—H3B108.2O3—C17—H17A110.1
O1—C4—C5115.30 (13)C2—C17—H17A110.1
O1—C4—C9124.24 (15)O3—C17—H17B110.1
C5—C4—C9120.46 (14)C2—C17—H17B110.1
C6—C5—C4119.95 (15)H17A—C17—H17B108.4
C6—C5—H5120.0O3—C18—C19115.40 (16)
C4—C5—H5120.0O3—C18—C23124.55 (15)
C7—C6—C5120.12 (17)C19—C18—C23120.05 (16)
C7—C6—H6119.9C20—C19—C18119.78 (19)
C5—C6—H6119.9C20—C19—H19120.1
C8—C7—C6119.77 (16)C18—C19—H19120.1
C8—C7—H7120.1C21—C20—C19120.70 (19)
C6—C7—H7120.1C21—C20—H20119.7
C7—C8—C9121.14 (17)C19—C20—H20119.7
C7—C8—H8119.4C22—C21—C20119.31 (19)
C9—C8—H8119.4C22—C21—H21120.3
C4—C9—C8118.54 (17)C20—C21—H21120.3
C4—C9—H9120.7C21—C22—C23121.0 (2)
C8—C9—H9120.7C21—C22—H22119.5
O2—C10—C2108.21 (12)C23—C22—H22119.5
O2—C10—H10A110.1C18—C23—C22119.18 (18)
C2—C10—H10A110.1C18—C23—H23120.4
O2—C10—H10B110.1C22—C23—H23120.4
C2—C10—H10B110.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O2i0.932.593.5081 (19)170
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O2i0.932.593.5081 (19)170.0
Symmetry code: (i) x, y+1, z.
Acknowledgements top

We gratefully acknowledge King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia for use of the X-ray diffraction facility.

references
References top

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Laliberté, D., Maris, T. & Wuest, J. D. (2003). Acta Cryst. E59, o799–o801.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

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