supplementary materials


kj2224 scheme

Acta Cryst. (2013). E69, o1080    [ doi:10.1107/S1600536813015687 ]

Bis(ethyleneglycolato-[kappa]2O,O')tellurium(IV)

N. R. Brooks, M. Wu, L. Van Meervelt, K. Binnemans and J. Fransaer

Abstract top

The title compound, C4H8O4Te, crystallized from a solution of Te4+ in ethylene glycol. The TeIV atom is in a distorted seesaw coordination defined by four O atoms from two different ethyleneglycate ligands. The C atoms of the ethyleneglycate ligands are disorderd over two positions, with population parameters of 50.3 (6) and 49.7 (6)% indicating a statistical distribution. Due to the possibility to transform the primitive monoclinic unit cell into a metrically orthorhombic C unit cell, the data are twinned and were refined with the twin law -100/0-10/101 with the relative scale factor refining to 1.82 (4)% for the minor component.

Comment top

Solutions of Te4+ in ethylene glycol are interesting for the purposes of electrodeposition of Te and Te compounds (Nguyen et al., 2012, Wu et al., 2013). During such electrodeposition experiments we have noticed a large number of colourless crystals on the walls of the glass flask. We report here the crystal structure of these crystals.

The title compound, Te(C2H4O2)2, crystallized with one molecule in the asymmetric unit. The Te atom is in a distorted seesaw coordination defined by four O atoms from two different ethyleneglycato ligands (Fig. 1, Table 1). The carbon atoms of the ethyleneglycato ligands are disorderd over two positions, with the major component comprising 50.3 (6)% of the total. The angle between the best planes through atoms Te1—O1—C2—C3—O4 and Te1—O5—C6—C7—O8 is 85.4 (3)°. For the second position the angle between the best planes through Te1—O1—C7'—C6'—O8 and Te1—O4—C2'—C3'—O5 is 85.6 (3)°.

Crystal structures of seven similar four coordinate Te4+ complexes with oxo ligands have previously been reported by Day & Holmes (1981), Yosef et al. (2007), Annan et al. (1992), Fleischer & Schollmeyer (2001), Betz et al. (2008) and Lindqvist (1967), all of which have a distorted seesaw geometry of the Te centre. The geometries or the Te—O bond lengths in these structures do not differ remarkably from those in the title compound. The most closely related compound is the octamethyl derivative bis(1,1,2,2-tetramethyleneglycolato-O,O')tellurium(IV) (Day & Holmes, 1981), in which the Te—O bond lengths are, within error, the same as in the title compound. The O—Te—O bond angles that define the seesaw are 105.59° and 153.53° compared to 94.83 (14)° and 159.65 (13)° in the title compound. In tetrakis(methoxy)tellurium(IV) (Betz et al., 2008), the O—Te—O bond angles are 89.99° and 171.42°.

Related literature top

For the use of Te4+ ethylene glycol solutions in electrodeposition of Te and Te compounds, see: Nguyen et al. (2012); Wu et al. (2013). For crystal structures of related four-coordinate Te4+ complexes with oxo ligands, see: Day & Holmes (1981); Yosef et al. (2007); Annan et al. (1992); Fleischer & Schollmeyer (2001); Betz et al. (2008); Lindqvist (1967).

Experimental top

Equal volumes of a 1 M solution of TeCl4 in ethylene glycol and a 4 M solution of AgNO3 in ethylene glycol were mixed together, ensuring that AgNO3 was in a slight excess. The resulting precipitate of AgCl was removed by filtration. Excess Ag+ ions in the remaining solution were removed by electrodeposition on a Pt working electrode at a constant potential of -0.1 V versus Ag and the solution used in electrodeposition experiments (Wu et al., 2013). When the solution was left to stand for a period of two months, a large number of colourless crystals of the title compound slowly appeared on the walls of the glass flask.

Refinement top

The H atoms were included using a riding model, with C—H distances of 0.99 Å and Uiso(H) = 1.2Ueq(C). The disorder of the ligands was modelled with two atomic positions for each C atom and the relative occupancy of these two positions refined as a least-squares parameter. The population parameters of 50.3 (6) and 49.7 (6)% indicate a statistical distribution. Constraints were applied to the displacement parameters of the C atoms to keep the respective atoms from the two disorder components the same. The unit-cell dimensions are such that it is possible to transform the primitive monoclinic unit cell into a metrically orthorhombic C unit cell, however the high Rint for the higher Laue class shows that the Laue symmetry of the data is unequivocally monoclinic. There is however slight twinning due to these metrics and the data were refined with the twin law 1 0 0 / 0 1 0 / 1 0 1 with the relative scale factor refining to 1.82 (4)% for the minor component.. At the end of the refinement there was a residual difference electron density peak of 3.93 e Å-3, which was located close to the Te atom. Although careful consideration was given to the unit cell determination and the absorption correction, this peak could not be eliminated.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. View of the asymmetric unit of Te(OCH2CH2O)2 showing the molecular structure and the disorder of the ligands. Solid bonds belong to one disorder component and open bonds to the other component (Te—O bonds are common to both components). For emphasis and to avoid confusion it should be noted that the (OCH2CH2O) ligands are disordered and the ligand is not macrocyclic.
Bis(ethyleneglycolato-κ2O,O')tellurium(IV) top
Crystal data top
C4H8O4TeF(000) = 464
Mr = 247.70Dx = 2.600 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.4838 (7) ÅCell parameters from 1495 reflections
b = 6.4978 (8) Åθ = 2.8–29.0°
c = 15.3633 (15) ŵ = 4.64 mm1
β = 102.168 (11)°T = 100 K
V = 632.72 (12) Å3Block, colourless
Z = 40.20 × 0.10 × 0.08 mm
Data collection top
Agilent SuperNova (Single source at offset, Eos)
diffractometer
1501 independent reflections
Radiation source: SuperNova (Mo) X-ray Source1291 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.031
Detector resolution: 15.9631 pixels mm-1θmax = 28.9°, θmin = 3.1°
ω scansh = 87
Absorption correction: numerical
(CrysAlis PRO; Agilent, 2012)
k = 88
Tmin = 0.540, Tmax = 0.710l = 2018
2841 measured reflections
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.034P)2]
where P = (Fo2 + 2Fc2)/3
1501 reflections(Δ/σ)max = 0.001
96 parametersΔρmax = 3.93 e Å3
0 restraintsΔρmin = 0.97 e Å3
Crystal data top
C4H8O4TeV = 632.72 (12) Å3
Mr = 247.70Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.4838 (7) ŵ = 4.64 mm1
b = 6.4978 (8) ÅT = 100 K
c = 15.3633 (15) Å0.20 × 0.10 × 0.08 mm
β = 102.168 (11)°
Data collection top
Agilent SuperNova (Single source at offset, Eos)
diffractometer
1501 independent reflections
Absorption correction: numerical
(CrysAlis PRO; Agilent, 2012)
1291 reflections with I > 2σ(I)
Tmin = 0.540, Tmax = 0.710Rint = 0.031
2841 measured reflectionsθmax = 28.9°
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.079Δρmax = 3.93 e Å3
S = 1.05Δρmin = 0.97 e Å3
1501 reflectionsAbsolute structure: ?
96 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*/UeqOcc. (<1)
Te10.47847 (4)0.12922 (6)0.711596 (17)0.00914 (12)
O10.2476 (5)0.3458 (6)0.6857 (2)0.0152 (8)
C20.1002 (15)0.2905 (17)0.6034 (6)0.0116 (15)0.499 (4)
H2A0.15430.33890.55130.014*0.499 (4)
H2B0.03850.35610.60160.014*0.499 (4)
C30.0770 (15)0.0595 (17)0.6007 (6)0.0132 (15)0.499 (4)
H3A0.01150.01470.64240.016*0.499 (4)
H3B0.00800.01460.53990.016*0.499 (4)
C2'0.3599 (14)0.2166 (17)0.5966 (6)0.0116 (15)0.501 (4)
H2'A0.29250.24440.53360.014*0.501 (4)
H2'B0.32730.33260.63320.014*0.501 (4)
C3'0.5943 (15)0.1981 (18)0.6060 (6)0.0132 (15)0.501 (4)
H3'A0.65780.33680.60670.016*0.501 (4)
H3'B0.62590.12110.55480.016*0.501 (4)
O40.2792 (5)0.0285 (6)0.6251 (2)0.0114 (7)
O50.6852 (6)0.0891 (6)0.6898 (2)0.0139 (8)
C60.7477 (16)0.0408 (18)0.6043 (6)0.0136 (15)0.499 (4)
H6A0.64120.09560.55380.016*0.499 (4)
H6B0.88530.10560.60300.016*0.499 (4)
C70.7640 (15)0.1902 (16)0.5960 (6)0.0101 (14)0.499 (4)
H7A0.89760.23970.63400.012*0.499 (4)
H7B0.76350.22800.53360.012*0.499 (4)
C6'0.4899 (15)0.4712 (18)0.5992 (6)0.0136 (15)0.501 (4)
H6'A0.50560.51060.53870.016*0.501 (4)
H6'B0.55540.57960.64130.016*0.501 (4)
C7'0.2586 (15)0.4511 (17)0.6011 (6)0.0101 (14)0.501 (4)
H7'A0.19200.58870.59870.012*0.501 (4)
H7'B0.18430.36940.54960.012*0.501 (4)
O80.5902 (5)0.2822 (6)0.6232 (2)0.0122 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Te10.00895 (18)0.0106 (2)0.00793 (17)0.00114 (12)0.00182 (13)0.00028 (12)
O10.0134 (18)0.020 (2)0.0122 (16)0.0023 (16)0.0029 (14)0.0021 (16)
C20.010 (3)0.015 (4)0.009 (3)0.003 (3)0.001 (3)0.000 (3)
C30.011 (3)0.015 (4)0.012 (3)0.003 (3)0.000 (3)0.002 (3)
C2'0.010 (3)0.015 (4)0.009 (3)0.003 (3)0.001 (3)0.000 (3)
C3'0.011 (3)0.015 (4)0.012 (3)0.003 (3)0.000 (3)0.002 (3)
O40.0091 (16)0.014 (2)0.0099 (15)0.0011 (15)0.0006 (13)0.0037 (15)
O50.0164 (18)0.012 (2)0.0121 (16)0.0035 (16)0.0014 (14)0.0012 (15)
C60.010 (3)0.016 (4)0.016 (3)0.006 (3)0.005 (3)0.006 (3)
C70.009 (3)0.009 (4)0.013 (3)0.001 (3)0.005 (3)0.002 (3)
C6'0.010 (3)0.016 (4)0.016 (3)0.006 (3)0.005 (3)0.006 (3)
C7'0.009 (3)0.009 (4)0.013 (3)0.001 (3)0.005 (3)0.002 (3)
O80.0137 (17)0.011 (2)0.0143 (16)0.0001 (16)0.0077 (14)0.0024 (16)
Geometric parameters (Å, º) top
Te1—O41.940 (3)C3'—O51.478 (10)
Te1—O81.942 (3)C3'—H3'A0.9900
Te1—O52.027 (3)C3'—H3'B0.9900
Te1—O12.032 (4)O5—C61.487 (10)
O1—C21.460 (10)C6—C71.512 (14)
O1—C7'1.484 (10)C6—H6A0.9900
C2—C31.509 (15)C6—H6B0.9900
C2—H2A0.9900C7—O81.414 (9)
C2—H2B0.9900C7—H7A0.9900
C3—O41.407 (10)C7—H7B0.9900
C3—H3A0.9900C6'—O81.402 (12)
C3—H3B0.9900C6'—C7'1.511 (12)
C2'—O41.434 (10)C6'—H6'A0.9900
C2'—C3'1.500 (12)C6'—H6'B0.9900
C2'—H2'A0.9900C7'—H7'A0.9900
C2'—H2'B0.9900C7'—H7'B0.9900
O4—Te1—O894.84 (14)C3—O4—C2'130.1 (6)
O4—Te1—O583.41 (15)C3—O4—Te1114.6 (5)
O8—Te1—O583.41 (15)C2'—O4—Te1115.2 (4)
O4—Te1—O182.81 (15)C3'—O5—C657.7 (6)
O8—Te1—O182.92 (14)C3'—O5—Te1108.8 (4)
O5—Te1—O1159.66 (13)C6—O5—Te1108.1 (5)
C2—O1—C7'59.9 (5)O5—C6—C7108.7 (7)
C2—O1—Te1108.7 (5)O5—C6—H6A110.0
C7'—O1—Te1108.7 (4)C7—C6—H6A110.0
O1—C2—C3108.2 (8)O5—C6—H6B110.0
O1—C2—H2A110.1C7—C6—H6B110.0
C3—C2—H2A110.1H6A—C6—H6B108.3
O1—C2—H2B110.1O8—C7—C6108.7 (7)
C3—C2—H2B110.1O8—C7—H7A109.9
H2A—C2—H2B108.4C6—C7—H7A109.9
O4—C3—C2108.4 (8)O8—C7—H7B109.9
O4—C3—H3A110.0C6—C7—H7B109.9
C2—C3—H3A110.0H7A—C7—H7B108.3
O4—C3—H3B110.0O8—C6'—C7'109.1 (8)
C2—C3—H3B110.0O8—C6'—H6'A109.9
H3A—C3—H3B108.4C7'—C6'—H6'A109.9
O4—C2'—C3'109.2 (8)O8—C6'—H6'B109.9
O4—C2'—H2'A109.8C7'—C6'—H6'B109.9
C3'—C2'—H2'A109.8H6'A—C6'—H6'B108.3
O4—C2'—H2'B109.8O1—C7'—C6'106.7 (7)
C3'—C2'—H2'B109.8O1—C7'—H7'A110.4
H2'A—C2'—H2'B108.3C6'—C7'—H7'A110.4
O5—C3'—C2'109.5 (7)O1—C7'—H7'B110.4
O5—C3'—H3'A109.8C6'—C7'—H7'B110.4
C2'—C3'—H3'A109.8H7'A—C7'—H7'B108.6
O5—C3'—H3'B109.8C6'—O8—C7130.3 (6)
C2'—C3'—H3'B109.8C6'—O8—Te1114.3 (4)
H3'A—C3'—H3'B108.2C7—O8—Te1115.4 (5)
O4—Te1—O1—C216.1 (5)O4—Te1—O5—C3'17.1 (5)
O8—Te1—O1—C279.7 (5)O8—Te1—O5—C3'78.5 (5)
O5—Te1—O1—C231.6 (7)O1—Te1—O5—C3'30.5 (7)
O4—Te1—O1—C7'79.7 (5)O4—Te1—O5—C678.3 (5)
O8—Te1—O1—C7'16.1 (5)O8—Te1—O5—C617.4 (5)
O5—Te1—O1—C7'32.0 (7)O1—Te1—O5—C630.7 (7)
C7'—O1—C2—C3138.3 (9)C3'—O5—C6—C7138.1 (10)
Te1—O1—C2—C337.0 (7)Te1—O5—C6—C736.9 (8)
O1—C2—C3—O445.4 (9)O5—C6—C7—O843.0 (10)
O4—C2'—C3'—O540.2 (10)C2—O1—C7'—C6'138.4 (10)
C2—C3—O4—C2'147.6 (8)Te1—O1—C7'—C6'37.2 (8)
C2—C3—O4—Te132.9 (8)O8—C6'—C7'—O146.5 (9)
C3'—C2'—O4—C3154.0 (8)C7'—C6'—O8—C7148.3 (8)
C3'—C2'—O4—Te126.5 (8)C7'—C6'—O8—Te134.5 (8)
O8—Te1—O4—C392.2 (5)C6—C7—O8—C6'153.6 (8)
O5—Te1—O4—C3175.0 (5)C6—C7—O8—Te129.2 (9)
O1—Te1—O4—C39.9 (5)O4—Te1—O8—C6'92.7 (5)
O8—Te1—O4—C2'88.2 (5)O5—Te1—O8—C6'175.5 (5)
O5—Te1—O4—C2'5.5 (5)O1—Te1—O8—C6'10.6 (5)
O1—Te1—O4—C2'170.5 (5)O4—Te1—O8—C789.7 (5)
C2'—C3'—O5—C6135.5 (11)O5—Te1—O8—C76.9 (5)
C2'—C3'—O5—Te135.5 (9)O1—Te1—O8—C7171.8 (5)

Experimental details

Crystal data
Chemical formulaC4H8O4Te
Mr247.70
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)6.4838 (7), 6.4978 (8), 15.3633 (15)
β (°) 102.168 (11)
V3)632.72 (12)
Z4
Radiation typeMo Kα
µ (mm1)4.64
Crystal size (mm)0.20 × 0.10 × 0.08
Data collection
DiffractometerAgilent SuperNova (Single source at offset, Eos)
diffractometer
Absorption correctionNumerical
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.540, 0.710
No. of measured, independent and
observed [I > 2σ(I)] reflections
2841, 1501, 1291
Rint0.031
(sin θ/λ)max1)0.679
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.079, 1.05
No. of reflections1501
No. of parameters96
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)3.93, 0.97

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top
Te1—O41.940 (3)Te1—O52.027 (3)
Te1—O81.942 (3)Te1—O12.032 (4)
Acknowledgements top

The authors acknowledge financial support by the KU Leuven (projects IDO/05/005 and GOA 08/05), by the FWO-Flanders (research community "Ionic Liquids") and by the IWT-Flanders (SBO369 project IWT 80031 "MAPIL") and experimental work performed by Hai P. Nguyen. The authors also thank the Hercules Foundation for supporting the purchase of the diffractometer through project AKUL/09/0035.

references
References top

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Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.

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Lindqvist, O. (1967). Acta Chem. Scand. 21, 1473–1483.

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