Syntheses and molecular structures of organo-tellurium(IV) halides trans-[(Ph2Te)(μ-Cl)2]n, cis-[(Ph2Te)(μ-Cl)2]n, [(p-MeC6H4)2TeBr2], and [{(p-MeC6H4)2TeBr}2(μ-O)]

Article abstract of DOI:10.1080/00958972.2018.1478085

Treatment of Ph₂Te with aqueous hydrogen chloride under air in refluxing THF gave trans-[(Ph₂Te)(μ-Cl)₂]_n (1), whereas interaction of Ph₂Te with ammonium chloride under similar condition afforded cis-[(Ph₂Te)(μ-Cl)₂]_n (2). Reaction of (p-MeC₆H₄)₂Te and bromine in refluxing THF resulted in formation of a discrete complex [(p-MeC₆H₄)₂TeBr₂] (3) with a step-like tetrameric structure, which further reacted with sodium hydroxide in refluxing THF to give a dinuclear tellurium oxide [{(p-Me-C₆H₄)₂TeBr}₂(μ-O)] (4) with a bridging oxygen atom. Complexes 1–4 have been spectroscopically characterized and their crystal structures have been established by X-ray crystallography.

Full text of DOI:10.1080/00958972.2018.1478085

Journal of Coordination Chemistry
ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://tandfonline.com/loi/gcoo20
Syntheses and molecular structures of organo-
tellurium(IV) halides trans-[(Ph2Te)(µ-Cl)2]n, cis-
[(Ph2Te)(µ-Cl)2]n, [(p-MeC6H4)2TeBr2], and [{(p-
MeC6H4)2TeBr}2(µ-O)]
Yu-Jie Cui, Feng Hu, Ai-Quan Jia, Zhi-Feng Xin & Qian-Feng Zhang
To cite this article: Yu-Jie Cui, Feng Hu, Ai-Quan Jia, Zhi-Feng Xin & Qian-Feng Zhang (2018):
Syntheses and molecular structures of organo-tellurium(IV) halides trans-[(Ph2Te)(µ-Cl)2]n, cis-
[(Ph2Te)(µ-Cl)2]n, [(p-MeC6H4)2TeBr2], and [{(p-MeC6H4)2TeBr}2(µ-O)], Journal of Coordination
Chemistry, DOI: 10.1080/00958972.2018.1478085
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Journal of Coordination Chemistry, 2018
https://doi.org/10.1080/00958972.2018.1478085
Syntheses and molecular structures of organo-tellurium(IV)
halides trans-[(Ph2Te)(μ-Cl)2]n, cis-[(Ph2Te)(μ-Cl)2]n,
[(p-MeC6H4)2TeBr2], and [{(p-MeC6H4)2TeBr}2(μ-O)]
Yu-Jie Cui, Feng Hu, Ai-Quan Jia, Zhi-Feng Xin and Qian-Feng Zhang
institute of molecular engineering and applied Chemistry, anhui university of technology, anhui, Pr China
ABSTRACT
ARTICLE HISTORY
received 5 april 2017
accepted 18 april 2018
Treatment of Ph2Te with aqueous hydrogen chloride under air in
refluxing THF gave trans-[(Ph2Te)(μ-Cl)2]n (1), whereas interaction
of Ph2Te with ammonium chloride under similar condition afforded
cis-[(Ph2Te)(μ-Cl)2]n (2). Reaction of (p-MeC6H4)2Te and bromine
in refluxing THF resulted in formation of a discrete complex [(p-
MeC6H4)2TeBr2] (3) with a step-like tetrameric structure, which further
reacted with sodium hydroxide in refluxing THF to give a dinuclear
tellurium oxide [{(p-Me-C6H4)2TeBr}2(μ-O)] (4) with a bridging oxygen
atom. Complexes 1–4 have been spectroscopically characterized and
their crystal structures have been established by X-ray crystallography.
KEYWORDS
tellurium; halide;
organotellurium; synthesis;
crystal structure
1. Introduction
The coordination chemistry of organotellurium compounds has attracted considerable
attention in recent years because of their potential application for organic syntheses [1] and
utilization in the semiconductor industry [2], along with their fascinating molecular and
supramolecular structures [3]. Owing to their inherent propensity, organotellurium com-
pounds can form non-covalent Te⋯X bonds (X=F, Cl, Br, I, N, O, S) in solution [4] and thus
produce secondary Te–X interactions affecting the coordination geometry of the tellurium
atoms [5]. In typical organotellurium halides and oxides, the tellurium can adopt different
CONTACT Qian-feng Zhang
zhangqf@ahut.edu.cn
© 2018 informa uK limited, trading as taylor & francis Group

2
Y.-J. CUI ET AL.
equally stable valence states and coordination modes [6–11]. The variation of number and
size of the organic substituents also influence the behavior, and these two factors may result
in the crystal engineering of organotellurium derivatives [12]. As part of our interest in this
chemistry, we have synthesized various organic tellurolate compounds [13]. In the course
of this work, we have isolated a series of organotellurium compounds from reactions in
solution. In this paper, syntheses and molecular structures of a series of organotellurium(IV)
halides trans-[(Ph2Te)(μ-Cl)2]n, cis-[(Ph2Te)(μ-Cl)2]n, [(p-MeC6H4)2TeBr2], and [{(p-MeC6H4)2-
TeBr}2(μ-O)] are reported, which can be placed into the pool of organotellurium reagents.
2. Experimental
2.1. General considerations
All syntheses were performed in oven-dried glassware under a purified nitrogen atmosphere
using standard Schlenk techniques. The solvents of tetrahydrofuran and chloroform, and
the chemicals of ammonium chloride, concentrated hydrochloric acid, bromine, sodium
hydroxide, PhBr, and p-MeC6H4Br were purchased from Sinopharm Chemical Reagent Co.,
Ltd. and used without further purification. Ph2Te and (p-MeC6H4)2Te were prepared according
to the literature methods [6, 14]. NMR spectra were recorded on a BrukerALX400 spectrom-
1
eter operating at 400 and 126.2 MHz for H and 125Te, respectively, at room temperature.
Chemical shifts (δ, ppm) were reported with reference to SiMe4 (1H) and Me2Te (125Te).
Elemental analyses were carried out using a Perkin-Elmer 2400 CHN analyzer.
2.2. Synthesis of polymeric trans-phenyl-tellurium(IV) dichlorides trans-[(Ph2Te)
(μ-Cl)2]n (1)
To a solution of Ph2Te (141 mg, 0.50 mmol) in THF (20 mL) was added an aqueous solution
of HCl (1.0 M, 1.0 mL), and the reaction mixture was refluxed for 4 h, producing a red solution.
The solvent was evaporated in vacuo and the residue was extracted with chloroform
(5 mL × 3). The filtrate gradually deposited well-formed crystals of 1 at room temperature
1
in two days. Yield: 166 mg, 94% (based on Te). H NMR (400 MHz, CDCl3): δ = 6.83–7.89
(m, 10H, Ph) ppm. 125Te NMR (126 MHz, CDCl3): δ = 920 ppm. Anal. for C12H10Cl2Te: calcd C
40.86, H 2.86%; found C 40.83, H 2.89%.
2.3. Synthesis of polymeric cis-phenyl-tellurium(IV) dichlorides cis-[(Ph2Te)(μ-Cl)2]n
(2)
To a solution of Ph2Te (141 mg, 0.50 mmol) in THF (15 mL) was added a saturated aqueous
solution of NH4Cl (1.0 mL), and the reaction mixture was refluxed for 6 h, producing a red
solution. The solvent was evaporated in vacuo and the residue was extracted with chloroform
(5 mL × 3). The filtrate gradually deposited well-formed crystals of 2 at room temperature
in a week. Yield: 159 mg, 90% (based on Te). 1H NMR (400 MHz, CDCl3): δ = 6.92–7.85 (m, 10H,
Ph) ppm. 125Te NMR (126 MHz, CDCl3): δ = 926 ppm. Anal. for C12H10Cl2Te: calcd C 40.86, H
2.86%; found C 40.81, H 2.84%.

JOURNAL OF COORDINATION CHEMISTRY
3
2.4. Synthesis of di(4-methylphenyl)-tellurium(IV) dibromides [(p-MeC6H4)2TeBr2]
(3)
To a solution of (p-MeC6H4)2Te (155 mg, 0.50 mmol) in THF (15 mL) was added a THF solution
of bromine (1.0 M, 0.5 mL), and the reaction mixture was refluxed for 4 h, producing a dark
red solution. The solvent was evaporated in vacuo and the residue was extracted with chlo-
roform (5 mL × 3). The filtrate gradually deposited well-formed crystals of 3 at room tem-
perature in two days. Yield: 202 mg, 86% (based on Te). 1H NMR (400 MHz, CDCl3): δ = 2.36
(s, 6H, CH3), 6.83–7.89 (m, 8H, Ph) ppm. 125Te NMR (126 MHz, CDCl3): δ = 930 ppm. Anal. for
C14H14Br2Te: calcd C 35.80, H 3.00%; found C 35.62, H 2.95%.
2.5. Synthesis of oxygen-bridged di(4-methylphenyl)-tellurium(IV) bromide
[{(p-MeC6H4)2TeBr}2(μ-O)] (4)
To a solution of 3 (94 mg, 0.20 mmol) in THF (20 mL) was added an aqueous solution of
sodium hydroxide (1.0 M, 0.1 mL), and the reaction mixture was refluxed for 2 h, producing
a dark red solution. The solvent was evaporated in vacuo and the residue was extracted with
chloroform (5 mL × 3). The filtrate gradually deposited well formed crystals of 4 at room
temperature in three days. Yield: 65 mg, 82% (based on Te). 1H NMR (400 MHz, CDCl3): δ =
2.28 (s, 12H, CH3), 6.97–8.26 (m, 16H, Ph) ppm. 125Te NMR (126 MHz, CDCl3): δ = 932 ppm.
Anal. for C28H28OBr2Te2: calcd C 42.27, H 3.55%; found C 42.23, H 3.58%.
2.6. X-Ray crystallography
A summary of crystallographic data and experimental details for trans-[(Ph2Te)(μ-Cl)2]n (1),
cis-[(Ph2Te)(μ-Cl)2]n (2), [(p-MeC6H4)2TeBr2] (3), and [{(p-MeC6H4)2TeBr}2(μ-O)] (4) is presented
in Table 1. Intensity data were collected on a Bruker SMART APEX 2000 CCD diffractometer
equipped with graphite-monochromated MoKα radiation (λ = 0.71073 Å) by using a ω scan
technique (2.29° < θ < 27.71° for 1, 2.29° < θ < 24.97° for 2, 1.60° < θ < 27.56° for 3, and
1.85° < θ < 25.00° for 4) at 296(2) K. The collected frames were processed with the software
Saint [15]. The data were corrected for absorption using the program Sadabs [16]. Structures
were solved by Direct Methods and refined by full-matrix least-squares on F2 using the Shelxtl
software package [17, 18]. All non-hydrogen atoms were refined anisotropically. The positions
of all hydrogen atoms were generated geometrically (Csp3-H = 0.97 and Csp2-H = 0.93 Å),
assigned isotropic displacement parameters, and allowed to ride on their respective parent
carbon atoms before the final cycle of least-squares refinement.
Crystallographic data for trans-[(Ph2Te)(μ-Cl)2]n (1), cis-[(Ph2Te)(μ-Cl)2]n (2), [(p-MeC6H4)2TeBr2]
(3) and [{(p-MeC6H4)2TeBr}2(μ-O)] (4) have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication nos. CCDC-1451907/1451908/1451909/1451910.
Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK [Fax: (+44)1233–336-033; E-mail: deposit@ccdc.cam.ac.uk].
3. Results and discussion
As shown in Scheme 1, treatment of Ph2Te with hydrogen chloride, under air, in refluxing
THF gave trans-[(Ph2Te)(μ-Cl)2]n (1), whereas the interaction of Ph2Te with ammonium chlo-
ride in refluxing THF afforded cis-[(Ph2Te)(μ-Cl)2]n (2). Both 1 and 2 were confirmed to be of

4
Y.-J. CUI ET AL.
Table 1. Crystallographic data and experimental details for trans-[(Ph2te)(μ-Cl)2]n (1), cis-[(Ph2te)(μ-Cl)2]n
(2), [(p-meC6h4)2teBr2] (3) and [{(p-meC6h4)2teBr}2(μ-o)] (4).
Compound
1
2
3
4
empirical formula
formula weight
Crystal system
space group
a, Å
b, Å
c, Å
C
12h10Cl2te
352.70
C12h10Cl2te
352.70
monoclinic
C2
18.109(9)
8.668(4)
3.8245(18)
100.950(8)
589.4(5)
2
1.987
296(2)
336
2.939
C14h14Br2te
469.67
monoclinic
P21/n
16.5963(18)
10.2473(11)
17.8978(19)
95.725(2)
3028.6(6)
8
2.060
296(2)
1760
7.219
C28h28oBr2te
795.52
monoclinic
C2/c
21.0711(15)
13.0240(9)
10.7900(8)
100.566(2)
4417(7)
4
1.815
296(2)
1512
4.767
monoclinic
P21/n
3.8198(12)
8.659(3)
17.762(6)
91.571(5)
587.3(3)
2
β, deg
V, Å3
Z
Dcalc., g cm−3
temperature, K
F(000), e
1.995
296(2)
336
2.949
μ(moKα), mm−1
total refln.
3552
1557
19,312
9966
independent refln.
Rint
1333
0.0542
998
0.0209
6893
0.0285
3821
0.0210
Parameters
R1a, wR2b [I ≥ 2σ(I)]
R1, wR2 (all data)
Goodness of fit (Gof)c
final max/min diff. peaks, e Å−3
flack parameter
70
57
311
152
0.0794, 0.1973
0.0872, 0.1999
1.511
+2.680/−2.287
–
0.0606, 0.1620
0.0606, 0.1620
1.141
+2.779/−1.914
0.5(1)
0.0465, 0.1353
0.0706, 0.1526
1.032
+0.777/−1.674
–
0.0348, 0.0993
0.0481, 0.1082
1.011
+1.112/−1.158
–
aR1 = Σ||Fo| – |Fc||/Σ|Fo|.
bwR2 = [Σw(|Fo2| – |Fc2|)2/Σw|Fo2|2]1/2
.
cGof = [Σw(|Fo| – |Fc|)2/(Nobs – Nparam)]1/2
.
a structural type of a one-dimensional polymeric chain. A compound [Ph2TeCl2], adopting
the 1D zigzag chains via the secondary Te⋯Cl contacts with the chloride of an adjacent
molecule, was isolated from the reaction of Ph2Hg with TeCl4 in refluxing benzene, and a
compound [PhTeCl3] was prepared from the reaction of in situ generated [Ph2Te] with SO2Cl2
[19]. It appears that the trans-product is formed in acid solution and the cis-product in neutral
solution in the presence of chloride ion. To our best knowledge, the trans-conformation of
Ar2TeCl2-type (Ar=aryl) complexes is quite rare according to CCDC search results. Treatment
of (p-MeC6H4)2Te with bromine in refluxing THF resulted in the formation of [(p-MeC6H4)-
2TeBr2] (3) with a step-like tetrameric structure. This complex reacts with NaOH in refluxing
THF to give a dinuclear complex [{(p-Me-C6H4)2TeBr}2(μ-O)] (4) with a bridging oxygen atom.
An analogous iodide complex [(p-MeOC6H4)2TeI2]2(μ-O) was synthesized from the reaction
of (p-MeO-C6H4)2TeO and (p-MeOC6H4)2TeI2 in a ratio of 1:1 in THF [5]. Complexes 1–4 are air
stable in both the solid state and solution. The 1H NMR spectra of 1–4 show multiple signals
at 6.8–8.3 ppm corresponding to the phenyl groups. The 1H NMR spectra of 3 and 4 show a
singlet at 2.36 and 2.28 ppm, respectively, corresponding to the methyl groups of the 4-tolyl
moieties. The 125Te-NMR signals for 1–4 in CDCl3 range from 920 to 932 ppm, which are
comparable to other reported diorganotellurium dichlorides [5].
The crystal structures of 1–4 have been established by X-ray crystallography. Selected
bond lengths and angles are given in Tables 2–5, respectively. Crystal structure of the
reported complex [Ph2TeCl2], obtained from the reaction of Ph2Hg with TeCl4, are orthor-
hombic, space group Pbca, with unit-cell dimensions a = 7.644(2), b = 18.160(3), c = 18.014(3)
Å, Z = 8 [19]. In this research, 1 crystallized in the monoclinic centrosymmetric space group

JOURNAL OF COORDINATION CHEMISTRY
5
Scheme 1. syntheses of 1–4.
Table 2. selected bond lengths (Å) and angles (°) for trans-[(Ph2te)(μ-Cl)2]n (1).
te(1)–C(1)
te(1)–Cl(1)#2
C(1)#1–te(1)–C(1)
C(1)–te(1)–Cl(1)
C(1)–te(1)–Cl(1)#3
Cl(1)#2–te(1)–Cl(1)
Cl(1)#2–te(1)–Cl(1)#3
2.350(9)
2.644(3)
180.0(7)
90.3(2)
88.8(3)
87.76(8)
180.0
te(1)–Cl(1)
2.656(2)
C(1)–te(1)–Cl(1)#2
C(1)–te(1)–Cl(1)#1
Cl(1)#1–te(1)–Cl(1)
Cl(1)#3–te(1)–Cl(1)
te(1)#4–Cl(1)–te(1)
91.2(3)
89.7(2)
180.0
92.24(8)
92.24(8)
note: symmetry transformations used to generate equivalent atoms: #1 − x, −y, −z + 1; #2 – x + 1, −y, −z + 1; #3 x − 1, y, z;
#4 x + 1, y, z.
Table 3. selected bond lengths (Å) and angles (°) for cis-[(Ph2te)(μ-Cl)2]n (2).
te(1)–C(11)
te(1)–Cl(1)#2
C(11)#1–te(1)–C(11)
C(11)–te(1)–Cl(1)#1
C(11)–te(1)–Cl(1)#2
Cl(1)#2–te(1)–Cl(1)#3
Cl(1)–te(1)–Cl(1)#3
2.346(9)
2.650(4)
83.3(8)
134.9(3)
131.9(3)
125.85(17)
92.27(12)
te(1)–Cl(1)
2.654(4)
C(11)–te(1)–Cl(1)
88.5(3)
90.7(7)
63.03(17)
125.93(17)
92.27(12)
C(11)–te(1)–Cl(1)#2
Cl(1)#1–te(1)–Cl(1)#3
Cl(1)–te(1)–Cl(1)#1
te(1)–Cl(1)–te(1)#4
note: symmetry transformations used to generate equivalent atoms: #1 −x, y, −z + 2; #2 x−1, y, z; #3 –x + 1, y, −z + 2; #4
x + 1, y, z.

6
Y.-J. CUI ET AL.
Table 4. selected bond lengths (Å) and angles (°) for [(p-meC6h4)2teBr2] (3).
te(1)–C(11)
te(2)–C(31)
2.109(6)
2.114(7)
te(1)–C(21)
te(2)–C(41)
2.119(6)
2.129(7)
te(1)–Br(1)
te(2)–Br(3)
2.6717(10)
2.6920(9)
98.6(2)
89.04(18)
89.62(18)
88.71(17)
87.74(17)
178.66(3)
te(1)–Br(2)
te(2)–Br(4)
2.6946(10)
2.6133(12)
98.3(3)
91.13(17)
89.04(17)
91.94(18)
92.32(18)
174.81(4)
C(11)–te(1)–C(21)
C(11)–te(1)–Br(1)
C(11)–te(1)–Br(2)
C(31)–te(2)–Br(4)
C(31)–te(2)–Br(3)
Br(1)–te(1)–Br(2)
C(31)–te(2)–C(41)
C(21)–te(1)–Br(1)
C(21)–te(1)–Br(2)
C(41)–te(2)–Br(4)
C(41)–te(2)–Br(3)
Br(4)–te(2)–Br(3)
Table 5. selected bond lengths (Å) and angles (°) for [{(p-meC6h4)2teBr}2(μ-o)] (4).
te(1)–o(1)
te(1)–C(21)
C(21)–te(1)–C(11)
C(21)–te(1)–Br(1)
o(1)–te(1)–C(11)
te(1)–o(1)–te(1)#1
1.983(2)
2.108(4)
96.8(2)
88.1(1)
89.2(1)
126.1(2)
te(1)–C(11)
te(1)–Br(1)
C(11)–te(1)–Br(1)
o(1)–te(1)–C(21)
o(1)–te(1)–Br(1)
2.120(4)
2.880(1)
91.4(1)
86.7(1)
174.9(1)
note: symmetry transformations used to generate equivalent atoms: #1 –x + 1, y, −z + ½.
Chart 1. Common coordination modes of diorganotellurium dihalides.
P21/n and 2 crystallized in the monoclinic space group C2, respectively. Usually diorganotel-
lurium dihalides adopt two coordination geometries taking into account the steric demand
of the stereochemically active lone pair, as shown in Chart 1 [5]. The reported polymeric
complex [Ph2TeCl2] revealed a 5 + 1 coordination geometry in the solid state, with an equa-
torial lone pair (type B, Chart 1) [19]. In both 1 and 2, the tellurium atoms adopt the 5 + 2
geometry with an equatorial lone pair. The tellurium atom in the former displays a trans-co-
ordinated mode, whereas the central tellurium atom in the latter exhibits a cis-coordinated
mode, indicated by the angles C-Te-C (180.0(7)° for 1 and 83.3(8)° for 2) and four angles
Cl-Te-Cl at 87.76(8)°, 92.24(8)°, and 180.0° for 1 and at 63.04(17)°, 92.27(12)°, 125.93(17)°, and
125.85(17)° for 2. Both complexes show one-dimensional polymeric structures, as displayed
in Figures 1(b) and 2(b). There is a head-to-head arrangement of phenyl rings located on
two sides of the chain in 1, and there is a face-to-face arrangement of phenyl rings located
on one side of the chain in 2. The average bridging Te-Cl bond lengths are 2.651(2) Å and
2.652(2) Å for 1 and 2, respectively, slightly longer than the terminal Te–Cl bond lengths in
[(p-MeOC6H4)2TeCl2] (av. 2.516(2) Å) [20] and [(p-MeC6H4)2TeCl2] (av. 2.515(2) Å) [5]. The Te–
Cl–Te angles are 92.24(8)° and 92.3(1)° for 1 and 2, respectively. The Te–C bond lengths for
1 (2.350(9) Å) and 2 (2.346(9) Å) are longer than the values reported for other R2TeX2

JOURNAL OF COORDINATION CHEMISTRY
7
Figure 1. (a) structure of trans-[(Ph2te)(μ-Cl)2]n (1) showing the atom numbering scheme. the atoms are
drawn with 50% probability ellipsoids. (b) Perspective view of trans-[(Ph2te)(μ-Cl)2]n (1) showing chains
with head-to-head contacts of benzene rings. (c) Packing diagram of trans-[(Ph2te)(μ-Cl)2]n (1) in the bc
plane, showing the weak interactions of C–h⋯Cl van der Waals contacts (dashed lines) between the
neighboring chains. (d) Packing diagram of trans-[(Ph2te)(μ-Cl)2]n (1) in the ab plane, showing a two-
dimensional framework formed by the C–h⋯Cl van der Waals contacts (dashed lines).
complexes, such as [(p-MeC6H4)2TeCl2] (av. 2.116(3) Å) [5], [(C6H5)2TeCl2] (av. 2.111(7) Å) [19],
[(p-MeOC6H4)2TeCl2] (av. 2.113(6) Å) [20], and [Ph2TeF2] (av. 2.115(3) Å) [21]. Moreover, the
Te–C bond lengths in 1 and 2 are expectedly longer than the corresponding Se–C bond
length (1.938(3) Å) in the Se analog [Ph2SeCl2] [22]. Packing diagrams of 1 in the bc and ab
planes are presented in Figures 1(c) and (d), respectively, showing weak C-H⋯Cl van der
Waals contacts (H⋯Cl = 2.879(3) Å, C⋯Cl = 3.803(3) Å, ∠C–H⋯Cl = 172.4(2)°) between neigh-
boring chains, which results in the formation of a two-dimensional framework, as displayed
in Figure 1(d). Similar interactions were also observed in 2, as shown in Figures 2(c) and (d).
The C⋯Cl distance and the C–H⋯Cl angle are 3.806(4) Å and 170.0(4)°, respectively, which
are comparable with those in 1.
Complex 3 crystallized in the monoclinic space group P21/n with two crystallographically
independent [(p-MeC6H4)2TeBr2] molecules associated as symmetry related pairs by second
-
aryTe···Br interactions, as illustrated in Figure 3. Taking into account the steric demand of the
stereochemically active lone pair, the geometry of the two tellurium atoms is described as
pseudo-pentagonal-bipyramidal (type A, Chart 1), forming a discrete tetramer, which is similar
to that observed in complex [(p-MeC6H4)2TeCl2] [5]. Actually, this 5 + 2 coordination geometry

8
Y.-J. CUI ET AL.
Figure 2. (a) structure of cis-[(Ph2te)(μ-Cl)2]n (2) showing the atom numbering scheme. the atoms are
drawn with 50% probability ellipsoids. (b) Perspective view of cis-[(Ph2te)(μ-Cl)2]n (2) showing chains
with the face-to-face contacts of benzene rings. (c) Packing diagram of cis-[(Ph2te)(μ-Cl)2]n (2) in the
bc plane, showing the weak interactions of C–h⋯Cl van der Waals contacts (dashed lines) between
the neighboring chains. (d) Packing diagram of cis-[(Ph2te)(μ-Cl)2]n (2) in the ab plane, showing a two-
dimensional framework formed by the C–h⋯Cl van der Waals contacts (dashed lines).
Figure 3. (a) orteP plot of the two independent molecules of [(p-meC6h4)2teBr2] (3). the atoms are drawn
with 50% probability ellipsoids. (b) Perspective view of the two pairs of crystallographically independent
molecules of [(p-meC6h4)2teBr2] (3) associated by secondary te⋯Br interactions (dashed lines).
is the most frequently encountered for diorganotellurium dihalides [4]. The Br atoms occupy
the axial positions with Br–Te–Br angles of 178.66(3)° and 174.81(4)°. The angles between
the equatorial aryl groups (98.6(2)°, 98.3(3)°) are less than the normal 120°, presumably due

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9
Figure 4. (a) orteP drawing of [{(p-meC6h4)2teBr}2(μ-o)] (4) with 50% probability thermal ellipsoids. (b)
Perspective view of four molecules of [{(p-meC6h4)2teBr}2(μ-o)] (4) showing the association into one-
dimensional zigzag chain by secondary te⋯Br interactions (dashed lines).
to the repulsion of the aromatic groups by the equatorial lone pair, as predicted by valence
shell electron-pair repulsion (VSEPR) theory [5]. The Te4Br6 unit adopts a step-like structure
(see Figure 3(b)). A quite similar geometry was also found for the two independent tellurium
sites in the crystal structures of [(p-MeC6H4)2TeCl2] [5] and [(p-MeOC6H4)2TeCl2] [20]. The aver-
age Te–C bond length for 3 (2.118(6) Å) agrees well with those reported for other R2TeX2
complexes [5, 19–21, 23, 24], but is still shorter than the values for 1 (2.349(8) Å) and 2 (2.368(6)
Å). The average C–Te–C bond angle for 3 (98.4(3)°) is comparable with those reported for
[(p-MeOC6H4)2TeCl2] (96.46(2)°) [20], [(p-MeC6H4)2TeCl2] (99.16(11)°) [5] and [(C6H5)2TeCl2]
(99.01(29)°) [19]. The average Te–Br bond length and Br–Te–Br bond angle in 3 are 2.668(1)
Å and 176.74(4)°, respectively. The distances of the Te···Br secondary bonds in 3 are 3.704(8)
and 3.713(9) Å, which are shorter than that of 3.936(3) Å in [(C6H5)2TeBr2] [25].
Complex 4 crystallized in the monoclinic space group C2/c, with crystallographic sym-
metry as shown in Figure 4(a). The [{(p-MeC6H4)2TeBr}2(μ-O)] units are linked by the bromide
ions, leading to association into zigzag chains through Te···Br secondary interactions, as
illustrated in Figure 4(b). Taking into account the stereochemically active lone pair, the spatial

10
Y.-J. CUI ET AL.
arrangement around the tellurium atoms is pseudo-trigonal-bipyramidal with a C2BrO donor
set. The axialTe–Br bond length is 2.880(1) Å and the separation of theTe···Br atoms is 3.540(2)
Å. The Te–O bond length of 1.983(2) Å in 4 is in agreement with that of 1.986(6) Å in [{(p-Me-
OC6H4)2Te}2(μ-O)I2] [7], but is somewhat shorter than the Te–O single bond of the polymeric
complex [(p-MeOC6H4)2TeO]n (2.063(2) Å) [26]. The average Te-C bond length for 4 (2.114(4)
Å) agrees well with those reported for other R2TeX2 complexes and 3 (2.118(6) Å), but is still
shorter than the values for 1 (2.349(8) Å) and 2 (2.368(6) Å). The Te–O–Te angle of 126.1(2)°
is more obtuse than those of 118.8(2)° and 120.2(3)° in [{(p-MeOC6H4)2Te}2(μ-O)I2] [7] and
[(p-MeO-C6H4)2Te]2O(O3SCF3)2 [27], respectively.
4. Conclusion
Four organotellurium(IV) halide complexes, trans-[(Ph2Te)(μ-Cl)2]n (1), cis-[(Ph2Te)(μ-Cl)2]n (2),
[(p-MeC6H4)2TeBr2] (3), and [{(p-MeC6H4)2TeBr}2(μ-O)] (4), have been isolated under controlled
conditions and characterized by X-ray crystallography. Complexes 1 and 2 show polymeric
chain structures, the former with the head-to-head arrangement of phenyl rings located on
two sides of chains and the latter with the face-to-face arrangement of phenyl rings located
on one same side of the chains, which further form two-dimensional hydrogen-bonded
frameworks due to the weak C–H⋯Cl van der Waals contacts between the neighboring
chains. The structure of 3 may be described as a discrete tetramer through Te···Br secondary
interactions, with the Te4Br6 unit adopting the step-like structural type, while the structure
of 4 can be described as [{(p-MeC6H4)2TeBr}2(μ-O)] units that are linked by the bromide ions,
leading to a zigzag chain through the Te···Br secondary interactions.
Acknowledgements
We thank reviewers and co-editor for their helpful suggestions during revision of this paper.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This project was supported by the Natural Science Foundation of China [grant number 21471003].
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