Bis[(4-methyl­phen­yl)ethyn­yl] telluride

Caracelli, I.; Zukerman-Schpector, J.; Pena, J.M.; Stefani, H.A.; Tiekink, E.R.T.

doi:10.1107/S1600536810006264

organic compounds

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Volume 66| Part 3| March 2010| Page o685

doi:10.1107/S1600536810006264

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Bis[(4-methylphenyl)ethynyl] telluride

Ignez Caracelli,^a ^* Julio Zukerman-Schpector,^b Jesus M. Pena,^c Hélio A. Stefani ^c and Edward R. T. Tiekink ^d

^aBioMat-Physics Department, Univ Estadual Paulista, UNESP, 17033-360 Bauru, SP, Brazil, ^bDepartment of Chemistry, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^cDepartamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São Paulo-SP, Brazil, and ^dDepartment of Chemistry, University of Malaya, Kuala Lumpur 50603, Malaysia
^*Correspondence e-mail: ignez@fc.unesp.br

(Received 14 February 2010; accepted 16 February 2010; online 24 February 2010)

The tellurium atom in the title bis-ethynyl telluride, Te(C₉H₇)₂ or C₁₈H₁₄Te, is located on a crystallographic twofold axis, the C—Te—C angle being 92.23 (15)°. The dihedral angle between the rings is 87.27 (7)°. In the crystal structure, molecules are connected in chains parallel to the b axis and mediated by C—H⋯π interactions.

Related literature

For the synthesis of bis-ethynyl tellurides, see: Gedridge et al. (1992 ); Engman & Stern (1993 ). For background to the motivation of studies into tellurium chemistry, see: Petragnani & Stefani (2007 ); Zukerman-Schpector et al. (2008 ). For related structures, see: Jones & Ruthe (2006 ). For searching the Cambridge Structural Database, see: Bruno et al. (2002 ). For background to Te⋯π interactions, see: Tiekink & Zukerman-Schpector (2009 ); Zukerman-Schpector & Haiduc (2002 ).

Experimental

Crystal data

C₁₈H₁₄Te
M_r = 357.89
Monoclinic, C 2/c
a = 25.8462 (8) Å
b = 4.8902 (2) Å
c = 11.3764 (3) Å
β = 100.316 (2)°
V = 1414.65 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.09 mm⁻¹
T = 100 K
0.27 × 0.13 × 0.09 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.617, T_max = 0.746
5433 measured reflections
1443 independent reflections
1350 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.055
S = 1.20
1443 reflections
88 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9a⋯Cgⁱ	0.98	2.62	3.573 (3)	163
Symmetry code: (i) x, y+1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810006264/hg2646sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006264/hg2646Isup2.hkl

checkCIF report

Comment top

Carbon–carbon bond formation for the preparation of symmetrical and unsymmetrical 1,3-diyne compounds is one of the most useful and important tools in modern organic chemistry. The construction of 1,3-diynes can be achieved either by intermolecular or intramolecular coupling of two similar or dissimilar alkynylic functionalities in the presence of organometallic complexes. However, the synthesis and use of bis-ethynyl tellurides are scarcely described in the literature (Gedridge et al., 1992, Engman & Stern, 1993) and their use in the detelluration reaction to afford 1,3-diynes is unknown until now. As part of our ongoing research into tellurium chemistry (Petragnani & Stefani, 2007; Zukerman-Schpector et al., 2008), the title compound, (I), was synthesized and its crystal structure determined.

The C—Te—C in (I), Fig. 1, angle of 92.23 (15) ° is close to the smallest value found for related diorganotellurium compounds, i.e. 92.30 (14) ° for Te[C(H)═C(H)Ph]₂ (Jones & Ruthe, 2006). A search in the CSD (Bruno et al. 2002) showed 225 hits for related compounds and a mean value of 96.0 ° for the C—Te(II)—C angle.

The molecules are linked in chains parallel to the b axis mediated in a large part through C–H···π interactions, Table 1 and Fig. 1. Short intermolecular Te–C interactions [e.g. Te···C2ⁱⁱ = 3.541 (3) Å for ii: x, -1+ y, z], indicative of Te···π interactions (Zukerman-Schpector & Haiduc, 2002; Tiekink & Zukerman-Schpector, 2009), are also noted as contributing to the stability of the chain.

Related literature top

For the synthesis of bis-ethynyl tellurides, see: Gedridge et al. (1992); Engman & Stern (1993). For background to the motivation of studies into tellurium chemistry, see: Petragnani & Stefani (2007); Zukerman-Schpector et al. (2008). For related structures, see: Jones & Ruthe (2006). For searching the Cambridge Structural Database, see: Bruno et al. (2002). For background to Te···π interactions, see: Tiekink & Zukerman-Schpector (2009); Zukerman-Schpector & Haiduc (2002).

Experimental top

To a stirred solution of 1-ethynyl-4-methylbenzene (0.35 g, 3.0 mmol) in THF (10 ml), n-BuLi (1.2 ml, 2.5 M, 3.0 mmol) was added dropwise at 195 K. After 20 min., freshly crushed tellurium powder (0.38 g, 3.0 mmol) was added in one lot while a stream of argon was passed through the open flask. The cooling bath was then removed to bring the reaction medium to room temperature. When almost all the tellurium was consumed, the reaction mixture was again cooled to 195 K. Then a solution of bromine (0.48 g, 3.0 mmol) in dry benzene (5 ml) was added dropwise, and stirring was continued for 15 min. The reaction mixture was hydrolyzed at 195 K by addition of water (5 ml). Dilution with water (20 ml) at room temperature, extraction with dichloromethane (2 x 15 ml), drying (MgSO₄), and flash chromatography (1/4 dichloromethane/hexane) afforded 0.90 g (62% yield) of the title compound as yellow crystals, m.pt. 400–401 K.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I) showing atom labelling scheme and displacement ellipsoids at the 50% probability level (arbitrary spheres for the H atoms). Symmetry operation i: -x, y, 3/2-z.
	Fig. 2. Supramolecular chain aligned along the b axis in (I) sustained by C–H···π interactions shown as orange dashed lines. Colour code: Te, purple; C, grey; and H, green.

bis[(4-methylphenyl)ethynyl] telluride top

Crystal data top

C₁₈H₁₄Te	F(000) = 696
M_r = 357.89	D_x = 1.680 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4746 reflections
a = 25.8462 (8) Å	θ = 2.2–27.7°
b = 4.8902 (2) Å	µ = 2.09 mm⁻¹
c = 11.3764 (3) Å	T = 100 K
β = 100.316 (2)°	Block, pale-yellow
V = 1414.65 (8) Å³	0.27 × 0.13 × 0.09 mm
Z = 4

Data collection top

Bruker SMART APEXII diffractometer	1443 independent reflections
Radiation source: sealed tube	1350 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 26.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −32→32
T_min = 0.617, T_max = 0.746	k = −6→5
5433 measured reflections	l = −14→14

Refinement top

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H-atom parameters constrained
S = 1.20	w = 1/[σ²(F_o²) + (0.019P)² + 5.1394P] where P = (F_o² + 2F_c²)/3
1443 reflections	(Δ/σ)_max < 0.001
88 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

C₁₈H₁₄Te	V = 1414.65 (8) Å³
M_r = 357.89	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 25.8462 (8) Å	µ = 2.09 mm⁻¹
b = 4.8902 (2) Å	T = 100 K
c = 11.3764 (3) Å	0.27 × 0.13 × 0.09 mm
β = 100.316 (2)°

Data collection top

Bruker SMART APEXII diffractometer	1443 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1350 reflections with I > 2σ(I)
T_min = 0.617, T_max = 0.746	R_int = 0.020
5433 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.055	H-atom parameters constrained
S = 1.20	Δρ_max = 0.74 e Å⁻³
1443 reflections	Δρ_min = −0.72 e Å⁻³
88 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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

	x	y	z	U_iso*/U_eq
Te	0.0000	0.37974 (5)	0.7500	0.01504 (9)
C1	0.04373 (10)	0.6695 (6)	0.8528 (2)	0.0161 (5)
C2	0.07098 (10)	0.8358 (6)	0.9095 (2)	0.0172 (6)
C3	0.10551 (10)	1.0424 (6)	0.9693 (2)	0.0155 (5)
C4	0.14665 (10)	1.1424 (6)	0.9162 (2)	0.0173 (6)
H4	0.1510	1.0759	0.8401	0.021*
C5	0.18087 (10)	1.3374 (6)	0.9737 (2)	0.0172 (6)
H5	0.2086	1.4024	0.9365	0.021*
C6	0.17559 (10)	1.4406 (6)	1.0852 (2)	0.0154 (6)
C7	0.13423 (10)	1.3430 (6)	1.1371 (2)	0.0179 (6)
H7	0.1298	1.4119	1.2127	0.022*
C8	0.09947 (10)	1.1478 (6)	1.0810 (2)	0.0170 (5)
H8	0.0715	1.0851	1.1181	0.020*
C9	0.21318 (10)	1.6531 (6)	1.1461 (2)	0.0189 (6)
H9A	0.1990	1.8358	1.1248	0.028*
H9B	0.2472	1.6332	1.1202	0.028*
H9C	0.2179	1.6286	1.2329	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Te	0.01487 (13)	0.01124 (14)	0.01834 (14)	0.000	0.00119 (9)	0.000
C1	0.0156 (12)	0.0148 (14)	0.0177 (12)	0.0001 (11)	0.0023 (10)	0.0042 (11)
C2	0.0154 (12)	0.0175 (15)	0.0183 (12)	0.0040 (11)	0.0021 (10)	0.0045 (12)
C3	0.0151 (12)	0.0123 (14)	0.0175 (12)	0.0018 (10)	−0.0013 (10)	0.0008 (11)
C4	0.0199 (12)	0.0172 (15)	0.0152 (12)	0.0024 (11)	0.0038 (10)	−0.0026 (12)
C5	0.0179 (12)	0.0163 (15)	0.0179 (13)	−0.0021 (11)	0.0049 (10)	0.0027 (12)
C6	0.0165 (12)	0.0116 (14)	0.0172 (12)	0.0021 (10)	0.0002 (10)	0.0009 (11)
C7	0.0204 (13)	0.0168 (15)	0.0168 (12)	0.0004 (11)	0.0037 (10)	−0.0020 (12)
C8	0.0180 (12)	0.0150 (14)	0.0192 (13)	−0.0016 (11)	0.0069 (10)	0.0037 (12)
C9	0.0182 (12)	0.0177 (15)	0.0199 (13)	−0.0015 (11)	0.0006 (10)	0.0035 (12)

Geometric parameters (Å, º) top

Te—C1	2.044 (3)	C6—C7	1.395 (4)
C1—C2	1.188 (4)	C6—C9	1.504 (4)
C2—C3	1.437 (4)	C7—C8	1.386 (4)
C3—C4	1.402 (4)	C7—H7	0.9500
C3—C8	1.406 (4)	C8—H8	0.9500
C4—C5	1.383 (4)	C9—H9A	0.9800
C4—H4	0.9500	C9—H9B	0.9800
C5—C6	1.394 (4)	C9—H9C	0.9800
C5—H5	0.9500

C1—Te—C1ⁱ	92.23 (15)	C7—C6—C9	121.5 (2)
C2—C1—Te	176.9 (2)	C8—C7—C6	121.6 (3)
C1—C2—C3	175.3 (3)	C8—C7—H7	119.2
C4—C3—C8	118.5 (3)	C6—C7—H7	119.2
C4—C3—C2	119.7 (3)	C7—C8—C3	120.1 (3)
C8—C3—C2	121.8 (3)	C7—C8—H8	120.0
C5—C4—C3	120.4 (3)	C3—C8—H8	120.0
C5—C4—H4	119.8	C6—C9—H9A	109.5
C3—C4—H4	119.8	C6—C9—H9B	109.5
C4—C5—C6	121.5 (3)	H9A—C9—H9B	109.5
C4—C5—H5	119.3	C6—C9—H9C	109.5
C6—C5—H5	119.3	H9A—C9—H9C	109.5
C5—C6—C7	117.9 (3)	H9B—C9—H9C	109.5
C5—C6—C9	120.6 (2)

C8—C3—C4—C5	1.0 (4)	C5—C6—C7—C8	0.5 (4)
C2—C3—C4—C5	−178.7 (3)	C9—C6—C7—C8	179.8 (3)
C3—C4—C5—C6	−0.2 (4)	C6—C7—C8—C3	0.2 (4)
C4—C5—C6—C7	−0.6 (4)	C4—C3—C8—C7	−1.0 (4)
C4—C5—C6—C9	−179.9 (3)	C2—C3—C8—C7	178.7 (3)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9a···Cgⁱⁱ	0.98	2.62	3.573 (3)	163

Symmetry code: (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄Te
M_r	357.89
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	25.8462 (8), 4.8902 (2), 11.3764 (3)
β (°)	100.316 (2)
V (Å³)	1414.65 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.09
Crystal size (mm)	0.27 × 0.13 × 0.09

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.617, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	5433, 1443, 1350
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.055, 1.20
No. of reflections	1443
No. of parameters	88
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.72

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9a···Cgⁱ	0.98	2.62	3.573 (3)	163

Symmetry code: (i) x, y+1, z.

Acknowledgements

We thank FAPESP (07/59404–2 to HAS), CNPq (472237/2008–0 to IC, 300613/2007 to HAS, and 306532/2009–3 to JZ-S) and CAPES (808/2009 to JZ-S and IC) for financial support.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o685

doi:10.1107/S1600536810006264

Open

access