Crystal structure of the first monomeric organotellurium(IV) Oxide: Bis(2-dimethylaminomethylphenyl)tellurium(IV) oxide

Article abstract of DOI:10.1080/10426500902947476

The crystal structure of (2-Me2NCH2C6H4)2TeO was determined by X-ray diffraction on a single crystal. The crystal symmetry is monoclinic, space group P21, with unit cell dimensions a = 9.2274(2), b = 10.1749(2), c = 11.5339(3)A,β= 109.952, V = 1017.90(4)A

Full text of DOI:10.1080/10426500902947476

This article was downloaded by: [Dalhousie University]
On: 12 March 2013, At: 07:58
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Phosphorus, Sulfur, and Silicon
and the Related Elements
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gpss20
Crystal Structure of the First
Monomeric Organotellurium(IV)
Oxide: Bis(2-
dimethylaminomethylphenyl)tellur
Oxide
Thomas M. Klapötke a , Burkhard Krumm a &
Matthias Scherr a
a Department of Chemistry and Biochemistry,
Ludwig-Maximilian University of Munich, Munich,
Germany
Version of record first published: 06 Jun 2009.
To cite this article: Thomas M. Klapötke , Burkhard Krumm & Matthias Scherr
(2009): Crystal Structure of the First Monomeric Organotellurium(IV) Oxide: Bis(2-
dimethylaminomethylphenyl)tellurium(IV) Oxide, Phosphorus, Sulfur, and Silicon and
the Related Elements, 184:6, 1347-1354
To link to this article: http://dx.doi.org/10.1080/10426500902947476
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-
and-conditions
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden.

The publisher does not give any warranty express or implied or make any
representation that the contents will be complete or accurate or up to
date. The accuracy of any instructions, formulae, and drug doses should be
independently verified with primary sources. The publisher shall not be liable
for any loss, actions, claims, proceedings, demand, or costs or damages
whatsoever or howsoever caused arising directly or indirectly in connection
with or arising out of the use of this material.

Phosphorus, Sulfur, and Silicon, 184:1347–1354, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902947476
Crystal Structure of the First Monomeric
Organotellurium(IV) Oxide:
Bis(2-dimethylaminomethylphenyl)tellurium(IV) Oxide
¨
Thomas M. Klapotke, Burkhard Krumm,
and Matthias Scherr
Department of Chemistry and Biochemistry, Ludwig-Maximilian
University of Munich, Munich, Germany
The crystal structure of (2-Me NCH C H ) TeO was determined by X-ray diffrac-
4 2
2
2 6
tion on a single crystal. The crystal symmetry is monoclinic, space group P2 , with
1
unit cell dimensions a = 9.2274(2), b = 10.1749(2), c = 11.5339(3) Å, β = 109.952◦,
V = 1017.90(4) Å3 and Z = 2. The structure has been solved and refined down
to wR = 0.0625, using 3675 independent reflections. The compound consists of
2
isolated molecules with two intramolecular Te· · ·N interactions of 2.565(4) and
2.755(6) Å stabilizing the tellurium atom.
Keywords Crystal structure; donor-stabilization; tellurium
INTRODUCTION
Organotellurium compounds containing intramolecular Te· · ·N inter-
actions have been investigated over the past years.1–16 In a re-
cent report, we were able to provide clear evidence for the exis-
tence of the tellurenyl fluoride 2-Me2NCH2C6H4TeF, with the help
of the stabilizing 2-dimethylaminomethylphenyl ligand.17 Besides
other synthesized organotellurium(IV) compounds with this spe-
cial nitrogen donor substituent, we also presented crystal struc-
tures of the organotellurium(IV) trifluoride 2-Me2NCH2C6H4TeF3,17
Received 29 April 2008; accepted 30 April 2008.
Dedicated to Professor Marian Mikolajczyk, CBMiM PAN in Lo´dz´, Poland, on the
ꢀ
ꢀ
occasion of his 70th birthday.
Financial support of this work by the University of Munich, the Fonds der Chemischen
Industrie and the Deutsche Forschungsgemeinschaft (KL 636/10−1) is gratefully ac-
knowledged.
Address correspondence to Thomas M. Klapo¨tke, Department of Chemistry and Bio-
chemistry, Ludwig-Maximilian University of Munich, Butenandtstr. 5–13(D), D-81377
Munich, Germany. E-mail: tmk@cup.uni-muenchen.de
1347

1348
T. M. Klapo¨tke et al.
the organotellurium(VI) oxofluoride salt [(2-Me2NCH2C6H4)2TeF3O]2-
[SiF6],17 and the organotelluronium salt [(2-Me2NCH2C6H4)2-
TeOH]2[SiF6],18 all characterized by intramolecular Te· · ·N secondary
interactions. To the best of our knowledge only a few examples for
crystal structures of organotellurium(IV) oxides exist, among others
Ph2TeO, (C6F5)2TeO and (p-MeOC6H4)2TeO.19–28 However, all struc-
tures have in common that they exist as dimers, tetramers, or poly-
mers with [Te(µ-O)]n (n = 2, 4, ∞) units. In this article, we present a
monomeric crystal structure of an organotellurium(IV) oxide.
RESULTS AND DISCUSSION
The title compound (2-Me2NCH2C6H4)2TeO was obtained as a hydrol-
ysis product of the corresponding organotellurium(IV) diazide, which
was prepared from the organotellurium(IV) difluoride with two equiv-
alents of Me3SiN3 according to Scheme 1.17
The hydrolysis of the diazide, resulting from an incompletely closed
vessel stored over a period of about 6 months, furnished the organo-
tellurium(IV) oxide (2Me2NCH2C6H4)2TeO. After a period of about 2
months, partially decomposition was already noticeable, which could
be proven by 125Te NMR spectroscopy. An additional resonance at
δ = 1160 ppm was found, which is shifted to lower field compared
to the corresponding organotellurium(IV) diazide (δ = 1090 ppm17) and
was, after the structure elucidation, assigned to the title compound.
Suitable single crystals were obtained from
a solution of
(2Me2NCH2C6H4)2Te(N3)2 in dichloromethane in a loosely closed vessel
at ambient temperature. The compound crystallizes in the monoclinic
crystal system, space group P21, with Z = 2 (see Figure 1).
The molecules exist as discrete monomers without significant in-
termolecular interactions below the sum of the tellurium–oxygen van
der Waals radii (vdWr TeO 3.58 Å).29 This is in contrast to known
structures of organotellurium(IV) oxides, which were reported to ex-
ist as dimers (Ph2TeO,28 (C6F5)2TeO,22,23 and OC(µ-NtBu)2TeO24) with
two different Te–O distances, one characteristic double bond and an
elongated coordinative bond, forming Te2O2 rings comprising bridging
SCHEME 1 Preparation of the tellurium(IV) diazide and the tellurium(IV)
oxide as the product of hydrolysis.

First Monomeric Organotellurium(IV) Oxide
1349
FIGURE 1 ORTEP plot of the crystal structure of (2-Me2NCH2C6H4)2TeO;
H atoms omitted for clarity. Selected bond lengths [Å] and angles [◦]: Te1–O1
1.8293(10), Te1–C1 2.118(5), Te1–C10 2.134(5), Te1· · ·N1 2.755(6), Te1· · ·N2
2.566(5), C1–Te1–C10 97.7(2), C1–Te1–O1 92.60(18), C10–Te1–O1 89.69(19),
O1–Te1· · ·N1 82.40(13), O1–Te1· · ·N2 159.66(17).
oxygen atoms. In case of (p-MeOC6H4)2TeO, a polymeric (TeO) chain
∞
with two slightly different Te–O distances is reported.21 The Te–O
distance in the title compound (1.829(1) Å) is slightly elongated com-
pared to the calculated value of monomeric Ph2TeO (1.814 Å),30 but
significantly shorter compared to the values for the tellurium oxygen
double bonds in the crystal structures of Ph2TeO (1.871(2) Å)28 and
(C6F5)2TeO (1.872(2)/1.87(1) Å).22,23 Due to the bridging character of
the oxygen atom in these compounds, the double bond character is re-
duced. This explains the elongated Te–O bonds compared to the bond
distance in the title compound and also compared to the calculated
monomeric Ph2TeO. The same findings with an elongated Te–O bond
distance with the 2-dimethylaminomethylphenyl substituent compared

1350
T. M. Klapo¨tke et al.
to the calculated value in the monomeric phenyl substituted compound
Ph2TeO were also reported previously for the hydroxytelluronium
cation [2-Me2NCH2C6H4TeOH]+ (calc.: 1.937 Å30 vs. exp.: 1.961(2) Å).18
Two intramolecular Te· · ·N contacts of 2.755(6) Å (Te1· · ·N1) and
2.565(4) Å (Te1· · ·N2), slightly elongated compared to the contact dis-
tance in 2-Me2NCH2C6H4TeF3 (2.405(4) Å)17 and considerably shorter
compared to the distances in (2-Me2NCH2C6H4)2Te (3.048/3.145 Å),8
are stabilizing the tellurium atom. These secondary interactions, sig-
nificantly shorter than the sum of the tellurium–nitrogen van der
Waals radii (vdWr TeN 3.61 Å29), are due to their sterical effects
on the tellurium atom likely the reason for the monomeric struc-
ture. The Te–C bonds are in the range of common tellurium–carbon
bond lengths (Te1–C1 2.117(5)/Te1–C10 2.135(5) Å vs. 2.099(4) Å in
2-Me2NCH2C6H4TeF317 and 2.12–2.20 Å in (C6F5)2TeO22,23). The C1–
Te1–C10 angle (97.78(18)◦) is more bent compared to the values in the
previously reported compounds (Ph2TeO: 91.8(6)◦28 and (C6F5)2TeO:
88.2(1)◦/88.6(5)◦22,23), which can also be explained as a result of the two
secondary contacts of the coordinating substituent. This leads to a dis-
torted octahedral arrangement around the tellurium atom, taking the
free valence electron pair of the tellurium atom into account. The coor-
dination of the aminomethyl nitrogen atoms creates two five-membered
heterocycles with four-coordinated amine moieties.
A view of the unit cell along the a-axis of the title compound is shown
in Figure 2. The packing can best be described as a layered structure
along the 21 screw axes in the [010] direction.
EXPERIMENTAL SECTION
General Remarks
All manipulations of air- and moisture-sensitive materials were per-
formed under an inert atmosphere of dry argon using flame-dried glass
vessels.31 The solvent dichloromethane was dried by standard meth-
ods stored under N2 and freshly distilled prior to use. All reagents
were used as received (Sigma-Aldrich, Fluka) if not stated otherwise.
NMR spectra were recorded on a JEOL Eclipse 400 instrument at 25◦C,
and chemical shifts were determined with respect to Me2Te (125Te,
126.1 MHz).
X-Ray Crystallography
For the compound, an Oxford Xcalibur3 diffractometer with a CCD
area detector was employed for data collection using Mo-Kα radiation

First Monomeric Organotellurium(IV) Oxide
1351
FIGURE 2 View of the unit cell of (2-Me2NCH2C6H4)2TeO along [100]; H
atoms omitted and only selected atoms labeled for clarity.
(λ = 0.71073 Å). The structure was solved using direct methods
(SIR9732) and refined by full-matrix least-squares on F2 (SHELXL33).
All non-hydrogen atoms were refined anisotropically. Satisfactory
atomic positions of the solvent molecules could not reliably be deter-
mined, therefore the disordered solvent was treated as a diffuse contri-
bution using the program SQUEEZE.34,35 SQUEEZE calculated 157 Å3 void
space per unit cell and 43 electrons; one molecule of dichloromethane re-
quires 42 electrons per unit cell. The absolute structure was determined
by refinement of the Flack parameter (Flack parameter = 0.04(3), 1585
Friedel pairs).36,37 See Table I. ORTEP plots are shown with thermal
ellipsoids at the 50% probability level. Crystallographic data for the
structure has been deposited with the Cambridge Crystallographic
Data Centre under the depository number CCDC-681994. Copies of
the data can be obtained free of charge upon application to The Direc-
tor, CCDC, 12 Union Road, Cambridge CB2 1EZ; UK (Fax: int. code
+(1223)336-033; e-mail for inquiry: fileserv@ccdc.cam.ac.uk; e-mail for
deposition: deposit@ccdc.cam.ac.uk).

1352
T. M. Klapo¨tke et al.
TABLE I Crystal and Structure Refinement Data
(2-Me2NCH2C6H4)2TeO
Empirical formula
Formula mass
C18H24N2O1Te
411.99
Temperature [K]
Crystal size [mm]
Crystal description
Crystal system
Space group
100
0.21 × 0.19 × 0.10
colorless block
monoclinic
P21
a [Å]
b [Å]
9.2274(2)
10.1749(2)
c [Å]
11.5339(3)
109.952(3)
β [◦]
V [Å3]
1778.0(2)
2
1.344
1.465
412
Z
ρ
[g cm−3
]
calc
µ [mm−1
F(000)
]
θ range [◦]
3.7–26.0
Index ranges
–10 ≤ h ≤ 11
–12 ≤ k ≤ 12
–14 ≤ l ≤ 12
5227
Reflcns collected
Reflcns observed
Reflcns unique
R1, wR2 (2σ data)
R1, wR2 (all data)
Max./min. transm.
Data/restr./param.
GOOF on F2
3205
3675 (Rint = 0.0245)
0.0273, 0.0615
0.0316, 0.0625
0.851/0.754
3675/0/203
0.984
Larg. diff. peak/hole [e/Å3]
0.307/–0.577
Formation of (2-Me2NCH2C6H4)2TeO
The reaction of (2-Me2NCH2C6H4)2TeF2 with two equivalents of
Me3SiN3 furnished the tellurium(IV) diazide (2-Me2NCH2C6H4)2
Te(N3)2.17 Single crystals of the tellurium oxide were obtained by stor-
ing a solution of the diazide in dichloromethane for 6 months in a loosely
closed glass vessel at ambient temperature.
125Te NMR (CDCl3) δ 1160 ppm.
REFERENCES
[1] L. Engman, A. Wojton, B. J. Oleksyn, and J. Sliwinski, Phosphorus, Sulfur, and
Silicon, 179, 285 (2004).

First Monomeric Organotellurium(IV) Oxide
1353
[2] G. Mugesh, A. Panda, S. Kumar, S. D. Apte, H. B. Singh, and R. J. Butcher,
Organometallics, 21, 884 (2002).
[3] J. E. Drake, M. B. Hursthouse, M. Kulcsar, M. E. Light, and A. Silvestru, J.
Organomet. Chem., 623, 153 (2001).
[4] A. Panda, G. Mugesh, H. B. Singh, and R. J. Butcher, Organometallics, 18, 1986
(1999).
[5] T. S. Butcher and M. R. Detty, J. Org. Chem., 63, 177 (1998).
[6] Z. Majeed, W. R. McWhinnie, and T. A. Hamor, J. Organomet. Chem., 549, 257
(1997).
[7] T. A. Hamor, H. Chen, W. R. McWhinnie, S. L. McWhinnie, and Z. Majeed, J.
Organomet. Chem., 523, 53 (1996).
[8] R. Kaur, H. B. Singh, and R. J. Butcher, Organometallics, 14, 4755 (1995).
[9] M. R. Detty, A. J. Williams, J. M. Hewitt, and M. McMillan, Organometallics, 14,
5258 (1995).
[10] M. R. Detty, A. E. Friedman, and M. McMillan, Organometallics, 13, 3338 (1994).
[11] A. G. Maslakov, W. R. McWhinnie, M. C. Perry, N. Shaikh, S. L. W. McWhinnie, and
T. A. Hamor, J. Chem. Soc., Dalton Trans., 619 (1993).
[12] H. B. Singh, N. Sudha, and R. T. Butcher, Inorg. Chem., 31, 1431 (1992).
[13] V. I. Minkin, I. D. Sadekov, A. A. Maksimenko, O. E. Kompan, and Y. T. Struchkov,
J. Organomet. Chem., 402, 331 (1991).
[14] H. B. Singh, N. Sudha, A. A. West, and T. A. Hamor, J. Chem. Soc., Dalton Trans.,
907 (1990).
[15] N. Al-Salim, A. A. West, W. R. McWhinnie, and T. A. Hamor, J. Chem. Soc., Dalton
Trans., 2363 (1988).
[16] M. A. K. Ahmed, A. E. McCarthy, W. R. McWhinnie, and F. J. Berry, J. Chem. Soc.,
Dalton Trans., 771 (1986).
[17] T. M. Klapo¨tke, B. Krumm, and M. Scherr, Z. Anorg. Allg. Chem., 633, 1618 (2007).
[18] T. M. Klapo¨tke, B. Krumm, and M. Scherr, Acta Crystallogr., E63, o4189 (2007).
[19] T. M. Klapo¨tke, B. Krumm, and M. Scherr, Acta Crystallogr., C64, m17 (2008).
[20] G. Schatte, T. Chivers, H. M. Tuononen, R. Suontamo, R. Laitinen, and J. Valkonen,
Inorg. Chem., 44, 443 (2005).
[21] J. Beckmann, D. Dakternieks, A. Duthie, F. Ribot, M. Schu¨rmann, and N. A. Lew-
cenko, Organometallics, 22, 3257 (2003).
[22] D. Naumann, W. Tyrra, R. Hermannn, I. Pantenburg, and M. S. Wickleder, Z. Anorg.
Allg. Chem., 628, 833 (2002).
[23] T. M. Klapo¨tke, B. Krumm, P. Mayer, H. Piotrowski, and O. P. Ruscitti, Z. Natur-
forsch., B57, 145 (2002).
[24] G. Schatte, T. Chivers, C. Jaska, and N. Sandblom, Chem. Commun., 1657 (2000).
[25] K. Kobayashi, N. Deguchi, O. Takahashi, K. Tanaka, E. Horn, O. Kikuchi, and N.
Furukawa, Angew. Chem., Int. Ed., 38, 1638 (1999).
[26] T. Chivers, M. Parvez, and G. Schatte, Inorg. Chem., 38, 5171 (1999).
[27] K. V. Domasevitch, V. V. Skopenko, and E. B. Rusanov, Z. Naturforsch., B51, 832
(1996).
[28] N. W. Alcock and W. D. Harrison, J. Chem. Soc., Dalton Trans., 709 (1982).
[29] A. Bondi, J. Phys. Chem., 68, 441 (1964).
[30] J. Beckmann, D. Dakternieks, A. Duthie, N. A. Lewcenko, C. Mitchell, and M.
Schu¨rmann, Z. Anorg. Allg. Chem., 631, 1856 (2005).
[31] D. F. Shriver and M. A. Drezdzon, The Manipulation of Air Sensitive Compounds
(Wiley, New York, 1986).

1354
T. M. Klapo¨tke et al.
[32] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, M. C.
Burla, G. Polidori, M. Camalli, R. Spagna, SIR97 (1997).
[33] G. M. Sheldrick, SHELXL, University of Go¨ttingen, Germany (1997).
[34] A. L. Spek, SQUEEZE, University of Utrecht, The Netherlands (2001).
[35] P. Van der Sluis and A. L. Spek, Acta Crystallogr., A46, 194 (1990).
[36] H. D. Flack and G. Bernardinelli, J. Appl. Crystallogr., 33, 1143 (2000).
[37] H. D. Flack, Acta Crystallogr., A39, 876 (1983).