Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101004656/na1512sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101004656/na1512Isup2.hkl |
CCDC reference: 166994
H atoms were located on stereochemical grounds and were refined riding on their carrier atoms, with an isotropic displacement parameter amounting to 1.5 (for methyl H atoms) or 1.2 (for the other H atoms) times the value of the equivalent isotropic displacement parameter of the atom the carrier atom.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: PARST95 (Nardelli, 1995), PLATON (Spek, 1998) and WinGX (Farrugia, 1999).
C11H11Cl3OTe | F(000) = 752 |
Mr = 393.15 | Dx = 1.859 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.661 (1) Å | Cell parameters from 25 reflections |
b = 6.0330 (8) Å | θ = 10.2–18.4° |
c = 18.4940 (2) Å | µ = 2.67 mm−1 |
β = 96.19 (1)° | T = 293 K |
V = 1404.4 (3) Å3 | Irregular, yellow |
Z = 4 | 0.40 × 0.25 × 0.20 mm |
Enraf-Nonius CAD-4 diffractometer | 2195 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.011 |
Graphite monochromator | θmax = 26.0°, θmin = 1.9° |
ω/–2θ scans | h = 0→15 |
Absorption correction: ψ scan (North, et al., 1968) | k = 0→7 |
Tmin = 0.394, Tmax = 0.587 | l = −22→22 |
2894 measured reflections | 3 standard reflections every 30 min |
2765 independent reflections | intensity decay: 0.8% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0332P)2 + 0.9575P] where P = (Fo2 + 2Fc2)/3 |
2765 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
C11H11Cl3OTe | V = 1404.4 (3) Å3 |
Mr = 393.15 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.661 (1) Å | µ = 2.67 mm−1 |
b = 6.0330 (8) Å | T = 293 K |
c = 18.4940 (2) Å | 0.40 × 0.25 × 0.20 mm |
β = 96.19 (1)° |
Enraf-Nonius CAD-4 diffractometer | 2195 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North, et al., 1968) | Rint = 0.011 |
Tmin = 0.394, Tmax = 0.587 | 3 standard reflections every 30 min |
2894 measured reflections | intensity decay: 0.8% |
2765 independent reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.52 e Å−3 |
2765 reflections | Δρmin = −0.48 e Å−3 |
146 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Te | 0.144145 (18) | 0.15391 (4) | 0.134876 (13) | 0.05104 (10) | |
Cl1 | 0.11439 (10) | 0.29239 (18) | 0.00597 (6) | 0.0701 (3) | |
Cl2 | 0.15327 (9) | −0.0258 (2) | 0.25671 (6) | 0.0785 (3) | |
Cl3 | −0.01838 (10) | 0.5037 (2) | 0.19260 (8) | 0.0890 (4) | |
O | 0.3449 (3) | 0.0173 (6) | 0.0954 (2) | 0.1007 (12) | |
C1 | −0.0197 (3) | 0.1178 (6) | 0.1290 (2) | 0.0537 (9) | |
H1 | −0.0508 | −0.0104 | 0.1084 | 0.064* | |
C2 | −0.0807 (3) | 0.2700 (6) | 0.15336 (19) | 0.0501 (8) | |
C3 | −0.1972 (3) | 0.2650 (7) | 0.1508 (2) | 0.0506 (8) | |
C4 | −0.2538 (3) | 0.4379 (8) | 0.1758 (2) | 0.0699 (11) | |
H4 | −0.2179 | 0.5633 | 0.1945 | 0.084* | |
C5 | −0.3632 (4) | 0.4284 (9) | 0.1736 (3) | 0.0792 (13) | |
H5 | −0.3999 | 0.5458 | 0.1917 | 0.095* | |
C6 | −0.4171 (4) | 0.2493 (10) | 0.1452 (3) | 0.0764 (13) | |
H6 | −0.4907 | 0.2440 | 0.1432 | 0.092* | |
C7 | −0.3622 (3) | 0.0760 (9) | 0.1194 (3) | 0.0780 (13) | |
H7 | −0.3991 | −0.0466 | 0.0994 | 0.094* | |
C8 | −0.2531 (3) | 0.0810 (7) | 0.1226 (2) | 0.0652 (10) | |
H8 | −0.2167 | −0.0392 | 0.1058 | 0.078* | |
C9 | 0.1809 (3) | −0.1600 (6) | 0.0912 (2) | 0.0606 (10) | |
H9A | 0.1668 | −0.2785 | 0.1243 | 0.073* | |
H9B | 0.1389 | −0.1852 | 0.0449 | 0.073* | |
C10 | 0.2968 (3) | −0.1500 (7) | 0.0816 (2) | 0.0618 (10) | |
C11 | 0.3460 (4) | −0.3516 (8) | 0.0529 (3) | 0.0775 (13) | |
H11A | 0.4139 | −0.3139 | 0.0376 | 0.116* | |
H11B | 0.3006 | −0.4085 | 0.0122 | 0.116* | |
H11C | 0.3553 | −0.4623 | 0.0903 | 0.116* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Te | 0.04700 (14) | 0.04624 (14) | 0.05870 (16) | −0.00455 (10) | 0.00029 (10) | −0.00840 (11) |
Cl1 | 0.0854 (7) | 0.0612 (6) | 0.0629 (6) | −0.0015 (5) | 0.0044 (5) | −0.0054 (5) |
Cl2 | 0.0745 (7) | 0.0886 (8) | 0.0697 (6) | 0.0038 (6) | −0.0043 (5) | 0.0109 (6) |
Cl3 | 0.0727 (7) | 0.0722 (7) | 0.1268 (11) | −0.0185 (6) | 0.0318 (7) | −0.0511 (7) |
O | 0.0586 (18) | 0.086 (2) | 0.158 (4) | −0.0196 (18) | 0.017 (2) | −0.031 (3) |
C1 | 0.053 (2) | 0.049 (2) | 0.057 (2) | −0.0028 (16) | −0.0031 (16) | −0.0100 (17) |
C2 | 0.057 (2) | 0.0464 (19) | 0.0471 (19) | −0.0063 (17) | 0.0085 (16) | −0.0054 (16) |
C3 | 0.054 (2) | 0.0500 (19) | 0.0490 (19) | −0.0009 (17) | 0.0115 (16) | 0.0016 (16) |
C4 | 0.065 (3) | 0.064 (3) | 0.082 (3) | 0.004 (2) | 0.014 (2) | −0.008 (2) |
C5 | 0.065 (3) | 0.082 (3) | 0.092 (3) | 0.013 (3) | 0.020 (2) | −0.007 (3) |
C6 | 0.051 (2) | 0.095 (3) | 0.086 (3) | 0.002 (3) | 0.018 (2) | 0.013 (3) |
C7 | 0.064 (3) | 0.078 (3) | 0.092 (3) | −0.016 (2) | 0.007 (2) | 0.001 (3) |
C8 | 0.058 (2) | 0.059 (2) | 0.080 (3) | −0.0044 (19) | 0.015 (2) | −0.009 (2) |
C9 | 0.060 (2) | 0.041 (2) | 0.081 (3) | −0.0017 (17) | 0.014 (2) | −0.0111 (19) |
C10 | 0.053 (2) | 0.062 (2) | 0.070 (3) | 0.000 (2) | 0.0050 (18) | −0.001 (2) |
C11 | 0.069 (3) | 0.078 (3) | 0.087 (3) | 0.008 (2) | 0.018 (2) | 0.003 (3) |
Te—C1 | 2.077 (4) | C3—C4 | 1.373 (6) |
Te—C9 | 2.130 (4) | C3—C8 | 1.388 (6) |
Te—Cl2 | 2.4918 (12) | C4—C5 | 1.382 (6) |
Te—Cl1 | 2.5158 (11) | C5—C6 | 1.353 (7) |
Cl3—C2 | 1.736 (4) | C6—C7 | 1.370 (7) |
O—C10 | 1.192 (5) | C7—C8 | 1.377 (5) |
C1—C2 | 1.310 (5) | C9—C10 | 1.498 (5) |
C2—C3 | 1.471 (5) | C10—C11 | 1.491 (6) |
C1—Te—C9 | 98.32 (14) | C4—C3—C2 | 122.1 (4) |
C1—Te—Cl2 | 87.16 (11) | C8—C3—C2 | 119.8 (4) |
C9—Te—Cl2 | 88.03 (13) | C3—C4—C5 | 121.1 (4) |
C1—Te—Cl1 | 86.47 (11) | C6—C5—C4 | 120.4 (5) |
C9—Te—Cl1 | 87.26 (13) | C5—C6—C7 | 119.4 (4) |
Cl2—Te—Cl1 | 171.46 (4) | C6—C7—C8 | 120.8 (5) |
C2—C1—Te | 122.0 (3) | C7—C8—C3 | 120.2 (4) |
C1—C2—C3 | 126.9 (3) | C10—C9—Te | 105.4 (3) |
C1—C2—Cl3 | 117.1 (3) | O—C10—C11 | 122.9 (4) |
C3—C2—Cl3 | 116.0 (3) | O—C10—C9 | 119.6 (4) |
C4—C3—C8 | 118.1 (4) | C11—C10—C9 | 117.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···Oi | 0.93 | 2.57 | 3.360 (6) | 144 |
C4—H4···Cl3 | 0.93 | 2.56 | 2.990 (4) | 109 |
C1—H1···Cl1ii | 0.93 | 2.77 | 3.626 (4) | 154 |
C11—H11C···Cl2iii | 0.96 | 2.87 | 3.674 (6) | 142 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H11Cl3OTe |
Mr | 393.15 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 12.661 (1), 6.0330 (8), 18.4940 (2) |
β (°) | 96.19 (1) |
V (Å3) | 1404.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.67 |
Crystal size (mm) | 0.40 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North, et al., 1968) |
Tmin, Tmax | 0.394, 0.587 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2894, 2765, 2195 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.071, 1.04 |
No. of reflections | 2765 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.48 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1995), PARST95 (Nardelli, 1995), PLATON (Spek, 1998) and WinGX (Farrugia, 1999).
Te—C1 | 2.077 (4) | Te—Cl2 | 2.4918 (12) |
Te—C9 | 2.130 (4) | Te—Cl1 | 2.5158 (11) |
C1—Te—C9 | 98.32 (14) | C1—Te—Cl1 | 86.47 (11) |
C1—Te—Cl2 | 87.16 (11) | C9—Te—Cl1 | 87.26 (13) |
C9—Te—Cl2 | 88.03 (13) | Cl2—Te—Cl1 | 171.46 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···Oi | 0.93 | 2.57 | 3.360 (6) | 144 |
C4—H4···Cl3 | 0.93 | 2.56 | 2.990 (4) | 109 |
C1—H1···Cl1ii | 0.93 | 2.77 | 3.626 (4) | 154 |
C11—H11C···Cl2iii | 0.96 | 2.87 | 3.674 (6) | 142 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x+1/2, y−1/2, −z+1/2. |
Organyltellurium trichlorides are quite insoluble in the solvents usually used for NMR studies. On the other hand, the corresponding diorganotellurium dichlorides are quite soluble, especially in chloroform. For this reason, the organyltellurium trichloride obtained from the reaction of TeCl4 with phenylethyne was treated with an excess of acetone giving the corresponding α-tellurium acetone dichloride which, in turn, was recrystallized from dichloromethane to give the title compound, (I). In order to overcome the problem that the NMR analysis give no indication of the stereochemistry of the double bond, an X-ray analysis of (I) was undertaken.
Fig. 1 shows that the addition reaction proceeds in a syn fashion to give the Z isomer only. The coordination around the TeIV atom is consistent with a pseudo-trigonal-bipyramidal bond configuration, with two Cl atoms occupying the axial positions, and the C atoms and the lone pair of electrons occupying the equatorial positions. This configuration is in complete agreement with the valence-shell electron-pair repulsion (VSEPR) model (Gillespie, 1972). The average quadruple angle, αE4, defined as: [(360 - Cl—Te—Cl) + (360 - C—Te—C)]/4, for the Te lone pair of electrons, is 112.6°, a value typical for TeX4E configurations (Zukerman-Schpector et al., 1996, and references therein). The Te–Cl axial lengths are 0.13 and 0.16 Å longer than the sum of the normal covalent radii (2.36 Å; Ziolo & Troup, 1983) and may be compared with the values found in related compounds (Zukerman-Schpector et al., 1995, 1996). The Te—C bond distances of 2.077 (4) and 2.130 (4) Å are slightly different than the predicted values of 2.037 and 2.142 Å obtained using Pauling's radii for Te (1.37 Å), Csp2 (0.667 Å) and Csp3 (0.772 Å) atoms (Pauling, 1960).
From the Te···C2 distance of 2.987 (4) Å and the carbon non-bonded radius of 1.25 Å (O'Keefe & Hyde, 1981), the non-bonded radius for the Te atom may be estimated to be 1.74 Å, a value close to that found in related compounds (Zukerman-Schpector et al., 1995, 1996, and references therein). The equatorial plane formed by atoms C1, C9, Cl3 and Cl2i [symmetry code: (i) 1/2 - x, 1/2 + y, 1/2 - z] is slightly distorted (r.m.s. deviation 0.0757 Å) and the Te atom is 0.261 (2) Å out of this plane towards the Cl1 atom. The phenyl ring makes a dihedral angle of 10.7 (2)° with the C1/C9/Cl3/Cl2i equatorial plane.
The Te atom makes three non-bonded interactions, two intramolecular [Te···O = 2.842 (3) Å and Te···Cl3 = 3.209 (1) Å] and one intermolecular [Te···Cl21 = 3.637 (1) Å], which are significantly shorter than the sum of the van der Waals radii (3.60 and 4.01 Å for Te···O and Te···Cl, respectively; Pauling, 1960). The last interaction links the molecules in a spiral fashion. These adjacent helices are extended into a three-dimensional supramolecular array by a C6—H6···Oi interchain interaction, as shown in Fig. 2 and Table 2, where several C—H···Cl interactions, corresponding to H···Cl contacts shorter than Pauling's van der Waal radii sum (3.01 Å; Pauling, 1960), are also listed.
Taking into account the secondary interactions of tellurium, the real coordination number increases to seven. In order to decide which would be the best description of the polyhedron, the following dihedral angles were calculated: C1,Cl1,C9/Cl1,C9,O = 46.9 (1)°, Cl1,Cl3,Cl21/Cl1,O,Cl21 = 41.3 (1)° and C9,Cl2,Cl21/C9,Cl21,O = 33.3 (2)°. Thus, following Kouba and Wreford (1976), the arrangement about the Te atom should be described as a distorted monocapped octahedron, with the O atom capping the Cl1/C9/Cl21 face.