Salts of Sterically Hindered Chalcogen-Varied Herz Cations Including Those with [Te3Cl14]2– and [Te4Cl18]2– Anions

Article abstract of DOI:10.1002/ejic.201701470

Salts of sterically hindered chalcogen-varied Herz cations with various anions were synthesized. 4,6-Di-tert-butyl-substituted 1,2,3-benzothiaselenazolium (2), 2,1,3-benzothiaselenazolium (3), and 1,2,3-benzodiselenazolium (4) were obtained from correspon

Full text of DOI:10.1002/ejic.201701470

A Journal of
Accepted Article
Title: Salts of Sterically-Hindered Chalcogen-Varied Herz Cations
Including Those with New Anions [Te3Cl14]2- and [Te4Cl18]2-
Authors: Alexander Yurievich Makarov, Irina Yu. Bagryanskaya, Yulia
M. Volkova, Makhmut M. Shakirov, and Andrey V. Zibarev
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201701470
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
Salts of Sterically-Hindered Chalcogen-Varied Herz Cations Including Those
with New Anions [Te3Cl14]2– and [Te4Cl18]2–
Alexander Yu. Makarov,*[a] Irina Yu. Bagryanskaya,[a],[b] Yulia M. Volkova,[a] Makhmut M.
Shakirov,[a] and Andrey V. Zibarev*[a],[c]
Abstract: Salts of sterically-hindered chalcogen-varied Herz cations with various anions were
synthesized.
4,6-Di-tert-butyl-substituted
1,2,3-benzothiaselenazolium
(2),
2,1,3-
benzothiaselenazolium (3) and 1,2,3-benzodiselenazolium (4) were obtained from corresponding
1,2,3-benzodithiazolium (1) or 2-bromo-4,6-di-tert-butylaniline (9) and isolated in the form of
salts with [Cl]– or / and [SbCl6]–. Reactions of prepared in situ N,N,Te-tris(trimethylsilyl)-2-
amino-3,5-di-tert-butyltellurophenole with SeCl4, S2Cl2 or SOCl2 resulted in elimination of Te
and formation of salts [4]2[TeCl6], [1]2[Te3Cl14] and [1]2[Te4Cl18] together with N-sulfinyl-2-
amino-3,5-di-tert-butylphenyltellurium trichloride 11; expected 2,1,3-benzothiatellurazolium (5)
and 2,1,3-benzoselenatellurazolium (6) were not observed. Compounds [1][Cl] (solvate with
CHCl3), [2][SbCl6], [3][SbCl6], [4][SbCl6], [4]2[TeCl6], [1]2[Te3Cl14], [1]2[Te4Cl18] and 11 were
structurally defined by X-ray diffraction. All [SbCl6]– salts were isomorphous, anions [Te3Cl14]2–
and [Te4Cl18]2– were previously unknown. Compound 11 revealed significantly shortened
intramolecular contact Te…O.
_____________________________________________________________________________
[a]
Institute of Organic Chemistry, Russian Academy of Sciences, 630090 Novosibirsk,
Russia
E-mail: makarov@nioch.nsc.ru
[b]
[c]
Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk,
Russia
Department of Physics, Novosibirsk State University, 630090 Novosibirsk, Russia
E-mail: zibarev@nioch.nsc.ru
Supporting information for this article containing additional synthetic and structural
data is available on the WWW under https:
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
Introduction
1,2,3-Benzodithiazoliums (Herz cations) and their Se congeners (Scheme 1) are important for
many fields of pure and applied chemistry.[1,2] Particularly, they are precursors of 1,2,3-
benzodichalcogenazolyls[1a,2,3] (Herz radicals; Scheme 1) and related radical anions[4] which are
promising building blocks in the design and synthesis of conductive, magnetic and
optoelectronic molecular materials.[1a,5,6,7] Replacement of S by Se strengthens the intermolecular
interactions in a crystalline state and, consequently, increases electrical conductivity and
magnetic exchange interactions. Stronger, as compared with S atom, spin-orbit coupling in Se
atom leads to magnetic anisotropy and can provoke canted antiferromagnetism. As a result,
many Se containing 1,2,3-dichalcogenazolyls are electrical conductors and low-temperature bulk
ferromagnets or canted antiferromagnets.[6]
The aforementioned effects should be stronger for Te congeners of Herz radicals. However,
reduction of the only known Te containing Herz cation, 1,2,3-benzothiatellurazolium 18
(Scheme 1), resulted in insoluble diamagnetic material.[2b] The reason might be formation of
dimers or coordination polymers via secondary bonding interactions Te…N well-known for
tellurium-nitrogen compounds.[2b,8] Lighter Herz radicals have no tendency to dimerize in liquid
or gas phase,[2a] although forming weakly bonded π-dimers in a crystalline state was observed for
many related chalcogen-nitrogen radicals.[2c,5d,5m,6h,6m,9]
Dimerization of Te containing Herz radicals might be prevented by bulky substituents, e.g.
tert-butyl groups (t-Bu), in their carbocycles. Additionally, introduction of these lipophilic
groups might increase solubility of Herz salts (normally chlorides) in organic solvents, as well as
their stability towards moisture.[10] It is also thought that steric hindering and replacing S by Se,
especially in the position 2, should stabilize Herz radicals towards oxygen.[3b,c] To the best of our
knowledge, the only known t-Bu containing Herz cation is 4,6-di-tert-butyl-1,2,3-
benzodithiazolium 1 (Scheme 1) isolated in the form of salts with anions [Cl]–, [SbCl6]– and
[AsF6]–.[3b,c,11]
In the present paper, original synthetic protocols for cation 1 and its Se congeners 2-4
(Scheme 1) were elaborated and then transferred onto synthesis of their Te analogs 5 and 6
(Scheme 1). However, the approaches performed well for 1-4 were unsuccessful for 5 and 6.
Instead, salts [4]2[TeCl6], [1]2[Te3Cl14] and [1]2[Te4Cl18] together with N-sulfinyl-2-amino-3,5-di-
tert-butylphenyltellurium trichloride 11 were obtained. Anions [Te3Cl14]2– and [Te4Cl18]2– were
previously unknown.
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
7
1
S
7a
3a
6
S
N
Se
Se
Se
N
2
Se
S
S
5
N
N
4
3
4
2
3
1
Te
Se
Te
S
S
S
N
N
H2N
NH2
6
5
7
Se
N
Te
Br
SiMe3
SiMe3
SiMe3
SiMe3
NH2
9
N
SiMe3
SiMe3
8
10
Te
N
TeCl3
Te
Te
SiMe3
SiMe3
N=S=O
H2N
NH2
SiMe3
13
12
11
S
Se
S
N
S
Se
Se
S
S
Se
Te
N
N
N
N
18
14
15
17
16
Scheme 1. Compounds and numbering.
Results and Discussion
Preparations
The general synthetic approach to Se containing Herz cations exploits reactions of 2-
aminothio/seleno phenols or their hydrochloride, acetyl and trimethylsilyl derivatives with
SOCl2, S2Cl2, H2SeO3, SeO2, SeOCl2 or SeCl4.[1b,2,12] Replacement of atom S by atom Se at the
position 2 can be achived by the action of H2SeO3 or SeO2.[6d,10b,12e] With SeO2, the approach also
covers neutral 1,2,3-dithiazoles.[13] Te containing cation 18 (Scheme 1) was prepared from
N,N,S-tris(trimethylsilyl)-2-aminothiophenole and TeCl4.[2b]
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
In this work, salt [2][Cl] was synthesized from its S congener [1][Cl][3c,11] and converted into
[2][SbCl6] by the action of SbCl5 (Scheme 2). Interestingly, salt [1][Cl] was enormously stable
toward hydrolysis.[10] After several minutes of refluxing in aqueous NaOH, only partial
hydrolysis was observed. Complete hydrolysis (Scheme 2) was achieved by 6-h reflux of [1][Cl]
with NaOH in ethanol.
1) PPh3, H2O
2) SeCl4
1) NaOH
2) O2
S
S
S
N
Cl-
S
NH2 H2N
1
[ ][Cl]
7
S
N
S
SbCl5
-
-
Se
Se
SbCl6
Cl
N
2
[ ][Cl]
2
[ ][SbCl6]
Scheme 2. Synthesis of [2][Cl] and [2][SbCl6].
For syntheses of 1-Se congeners 3 and 4 (Scheme 1) of 1 and 2, the silylated 2-
aminoselenophenole 8 was prepared in situ from aniline 9 and then treated with SOCl2 or
SeOCl2, respectively. Reaction of 8 with SOCl2 led to isomorphous mixture of [3][Cl] and [4]
[Cl], and treatment of this product with SbCl5 resulted in [3][SbCl6] and [4][SbCl6] also in the
form of isomorphous mixture. In contrast, reaction of 8 with SeOCl2 followed by addition of
SbCl5 gave pure [4][SbCl6] (Scheme 3). Pure [3][SbCl6] was prepared from [4][SbCl6] (Scheme
4).
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
1) 3t-BuLi
2) Se
3) Me3SiCl
Br
Se
N
Se
1) SeOCl2
2) SbCl5
SiMe3
SiMe3
-
Se
SbCl6
N
NH2
9
SiMe3
4
[ ][SbCl6]
8
SOCl2
Se
Se
-
Cl-
S
Se
Cl
+
N
N
3
4
[ ][Cl]
[ ][Cl]
SbCl5
Se
Se
-
-
S
Se
SbCl6
SbCl6
+
N
N
3
4
[ ][SbCl6]
[ ][SbCl6]
29%
71%
inseparable mixture
Scheme 3. Synthesis of [3][Cl], [4][Cl], [3][SbCl6] and [4][SbCl6].
1) S2Cl2
2) SbCl5
Se
Se
SeH
NH2
NaBH4
-
-
+
+
S SbCl6
Se SbCl6
N
N
[
4][SbCl6]
[
3][SbCl6]
Scheme 4. Synthesis of [3][SbCl6].
For syntheses of 1-Te congeners 5 and 6 (Scheme 1) of 1 and 2 these approaches were,
however, ineffective. Reaction of S2Cl2 with generated in situ silylated 2-aminotellurophenole 10
(on its archetype 13, see Supporting Information) was accompanied by elimination of Te (most
likely in the form of TeCl4) and the formation of [1][Cl] together with [1]2[Te3Cl14] (Scheme 5).
Reaction of 10 with SeCl4 afforded [4]2[TeCl6], whereas reaction with SOCl2 resulted in
[1]2[Te4Cl18] and acyclic compound 11 (Scheme 5). Earlier, for binary chlorotellurate anions
only [TeCl6]2–, [Te2Cl10]2–, [Te3Cl13]– and polymeric ([TeCl5]–)n and ([Te2Cl9]–)n were described,[14]
whereas [Te3Cl14]2– and [Te4Cl18]2– were unknown.
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European Journal of Inorganic Chemistry
S
N
S
N
2-
Cl-
Te3Cl14
S
S
+
1
[ ][Cl]
2
1
[ ]2[Te3Cl14]
S2Cl2
1) 3t-BuLi
2) Te
3) Me3SiCl
Br
Te
Se
SiMe3
SiMe3
SeCl4
2-
Se
TeCl6
N
NH2
9
N
SiMe3
2
10
4
[ ]2[TeCl6]
SOCl2
TeCl3
S
2-
Te4Cl18
S
+
N
N=S=O
2
11
1
[ ]2[Te4Cl18]
Scheme 5. Synthesis of [1][Cl], [1]2[Te3Cl14], [4]2[TeCl6], [1]2[Te4Cl18] and 11.
Previously, only elimination of atom H or group t-Bu was reported for the 1,2,3-
dithiazolium-closure reaction.[1,11] Tentatively, elimination of Te observed in this work (in the
presence of chlorinating agents, most likely in the form of TeCl4) may be attributed to a
weakness of Te–C bond as compared with S–C and Se–C linkages. Formation of [1]2[Te4Cl18]
can be tentatively explained by reaction of 10 with S2Cl2 formed as byproduct of chlorination of
10 by SOCl2. High ratio Te : 1 in the reaction mixture needed for the formation of [1]2[Te4Cl18]
might be a consequence of Te containing byproducts arising from the generation of 10.
Another approach to Te containing Herz cations might be the aforementioned chalcogen
exchange well known for 1,2,3-dithiazoliums[5k,5l,6d,6e,6l,6n,12e,15] and 1,2,3,5-dithiadiazoliums[16] with
replacement of S atom by Se atom. Recently, mutual exchange of Group 16 atoms (O, S, Se, Te)
in neutral 5-membered chalcogen-nitrogen heterocycles with 3 heteroatoms was described,[13,17]
particularly, selective transformation of 1,2,3-dithiazoles into 1,2,3-thiaselenazoles under the
action of SeO2 in DMF.[13] However, on treatment of [1][Cl] with excess of TeO2 in hot DMF the
starting salt disappeared but the desired transformation of 1 into 5 was not detected by solution
1H NMR which revealed no signals in the range 7.5-10 ppm characteristic of Herz cations.
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Since new compound 11 is of obvious interest for chalcogen-nitrogen chemistry, its rational
synthesis was attempted. However, interaction of a specially prepared ditelluride 12 with SOCl2
gave only unidentified products (Scheme 6).
1) 3t-BuLi
2) Te
3) NH4Cl
Te-Li+
NH2
Te
Te
Br
SOCl2
K3[Fe(CN)6]
11
H2N
NH2
NH2
9
12
Scheme 6. Attempted synthesis of 11.
X-ray structures
Structures of [1][Cl] (solvate with CHCl3), [2][SbCl6], [3][SbCl6] and [4][SbCl6] (Fig. 1),
[1]2[Te3Cl14], [1]2[Te4Cl18], [4]2[TeCl6] and 11 (Fig. 2), and isomorphous mixture of [3][SbCl6]
and [4][SbCl6] (see Supporting Information) were determined by X-ray diffraction (XRD).
Salts of cations 1,[11] 2, 3 and 4 with anion [SbCl6]– are isomorphous. Previously,
isomorphism was observed for salts of 1,2,3-benzodithiazolium (14) and 2,1,3-
benzothiaselenazolium (15) with anion [BF4]–.[2a] With anion [GaCl4]–, salts of 1,2,3-
benzothiaselenazolium (16) and 1,2,3-benzodiselenazolium (17) are isomorphous, whereas
crystal structures of 1,2,3-benzodithiazolium 14 and 1,2,3-benzothiatellurazolium (18) salts are
different.[2a,2b]
Neglecting t-Bu substituents, all Herz cations studied in this work were planar within 0.027
([2][SbCl6]), 0.029 ([3][SbCl6]), 0.034 ([4][SbCl6]), 0.099 ([1][Cl]), 0.036 and 0.039
([1]2[Te3Cl14], two crystallographically independent species), 0.028 ([1]2[Te4Cl18]), 0.037 and
0.047 ([4]2[TeCl6], two crystallographically independent species) Å.
Similarly to salts of the parent 1,2,3-benzodichalcogenazoliums 14-18,[2a,2b] varying of
chalcogen in cations 1-4 affects significantly only the bonds to the involved atoms together with
angles in heterocycle (Table 1).
Varying of anion [Cl]–, [SbCl6]– and [Te4Cl18)]2– affects the geometry of cation 1 only
slightly. The biggest difference of 0.04 Å was observed for the C7–C7a bond length, most likely
because of interaction with the anion in salt [1][SbCl6] (the distance Cl–H7 is 2.805 Å, the sum
of van der Waals (VdW) radii 2.85 Å; the distance Cl–C7a is 3.385 Å, the sum of VdW radii
3.45 Å).[18] Variation of the bond lengths in the heterocycle is less than 0.01 Å despite there are
slightly shortened contacts Cl…S in [1][SbCl6] (3.515 and 3.537 Å, the sum of VdW radii is 3.55
Å) and strongly shortened ones in [1][Cl] ∙ CHCl3 (2.955, 3.138 and 3.260 Å; Fig. 3) and
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
[1]2[Te4Cl18] (3.157 and 3.204 Å). Thus, 1,2,3-benzodithiazolium ring is structurally very rigid,
in striking contrast, for instance, to related 1,3,2,4-benzodithiadiazines.[19]
[1][Cl] ∙ CHCl3
[2][SbCl6]
[3][SbCl6]
[4][SbCl6]
Figure 1. XRD structures of [1][Cl] (solvate with CHCl3), [2][SbCl6], [3][SbCl6] and [4][SbCl6].
For selected bond lengths and angles in heterocycles and carbocycles, see Table 1 and
Supporting Information, respectively.
[1]2[Te4Cl18]
[1]2[Te3Cl14]
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[4]2[TeCl6]
11
Figure 2. XRD structures of [4]2[TeCl6], [1]2[Te3Cl14], [1]2[Te4Cl18] and 11. Selected bond
lengths (Å) and angles (o) (crystallographic numbering; for [4]2[TeCl6] and [1]2[Te3Cl14],
accuracy of determined coordinates of light atoms С and N was low and only S–S and Se–Se
bond lengths are given): [4]2[TeCl6]: Te1–Cl1 2.566(2), Te1–Cl2 2.355(6), Te1–Cl3 2.453(2),
Te1–Cl4 2.573(2), Te1–Cl5 2.471(2), Te1–Cl6 2.902(2), Se1–Se2 2.294(1), Se1A–Se2A
2.287(1); [1]2[Te3Cl14]: Te1–Cl5 2.801(3), Te1–Cl2A 2.323(3), Te1–Cl3A 2.365(4), Te1–Cl4A
2.477(3), Te1–Cl1A 2.484(4), Te1–Cl3B 3065(4), Te2–Cl1 2.914(4), Te2–Cl4 2.758(4), Te2–
Cl2B 2.350(4), Te2–Cl3B 2.609(4), Te2–Cl1B 2.393(4), Te2–Cl4B 2.400(4), Te3–Cl4 2.794(3),
Te3–Cl3C 2.353(4), Te3–Cl5 2.800(3), Te3–Cl2C 2.350(4), Te3–Cl1C 2.356(4), Te3–Cl1
2.799(4), S1A–S2A 2.020(4), S1B–S2B 2.024(4); [1]2[Te4Cl18] (for the cation, see Table 1):
Te3–Cl1S 2.899(1), Te3–Cl1 2.368(1), Te3–Cl2 2.354(1), Te3–Cl3S 2.833(1), Te3–Cl7
2.330(1), Te3–Cl2S 2.754(1), Te2–Cl1S 2.8644(8), Te2–Cl3S 2.791(1), Te2–Cl4 2.326(1), Te2–
Cl5 2.350(1), Te2–Cl6 2.365(1), Te2–Cl2S 2.775(1); 11: N1–S1 1.503(2), S1–O1 1.478(2), N1–
C1 1.400(3), C1–C6 1.411(3), C6–Te1 2.133(2), N1–S1–O1 118.0(1), C1–N1–S1 131.8(2), C6–
C1–N1 123.6(2), Te1–C6–C1 125.9(2).
Table 1. Selected bond lenghts (Å) and angles (o) for the heterocyclesa of cations of [1][SbCl6]
(E1 = E2 = S),[11] [2][SbCl6] (E1 = S, E2 = Se), [3][SbCl6] (E1= Se, E2 = S), [4][SbCl6] (E1 = E2
= Se), [1][Cl]b (E1= E2 = S) and [1]2[Te4Cl18] (E1 = E2 = S) (chemical numbering, Scheme 1).
[1][SbCl6]
[2][SbCl6]
[3][SbCl6]
[4][SbCl6]
[1][Cl]b
[1]2[Te4Cl18]
Bond / angle
C3a–N3
E1–E2
E2–N3
C3a–E1
C3a–C7a
C7a–E1–E2
E1–E2–N3
E2–N3–C3a
N3–C3a–C7a
1.346(7)
2.022(3)
1.571(5)
1.704(6)
1.435(8)
92.0(3)
99.7(2)
117.5(5)
115.4(6)
1.323(5)
2.156(1)
1.740(4)
1.708(4)
1.446(4)
93.0(1)
94.8(1)
116.3(2)
119.3(3)
1.339(4)
2.179(1)
1.602(3)
1.858(3)
1.433(4)
87.6(1)
99.5(1)
119.0(2)
118.5(3)
1.330(3)
2.2877(5)
1.746(2)
1.855(3)
1.443(4)
88.4(1)
95.51(8)
118.4(2)
120.3(2)
1.351(6)
2.030(2)
1.580(4)
1.707(4)
1.435(5)
92.0(1)
99.8(2)
116.9(3)
116.0(4)
1.338(5)
2.030(2)
1.578(3)
1.704(3)
1.431(4)
92.5(1)
99.1(1)
117.3(2)
116.6(3)
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C3a–C7a–E1
115.4(5)
116.6(3)
115.4(2)
117.4(2)
115.3(3)
114.5(2)
a For the carbocycles, see Supporting Information.
b Solvate with CHCl3.
Figure 3. XRD crystal structure of [1][Cl] ∙ CHCl3 featuring shortened contacts (Å) within (left)
and between (right) ion pairs.
The crystals of [1][Cl] ∙ CHCl3 consist of centrosymmetric dimers of the ion pairs (Fig. 3).
Interactions between dimers in crystal are weak since the only contacts between the dimers are
S…H with distance 2.928 Å which is longer than the sum of VdW radii (2.85 Å).[18b,18c] There are
also shortened contacts Cl…H between the anion and cation (2.63 Å, the sum of VdW radii is
2.85 Å) and between the anion and CHCl3 molecule (2.44 Å). The latter seems to be essential for
the dimer’s formation and solubility in partially chlorinated solvents. Isolation in the form of
solvate reveals an affinity of [1][Cl] for CHCl3 leading to its high solubility in CHCl3 or CH2Cl2
uncommon for 1,2,3-benzodithiazolium chlorides without lipophilic substituents in cations. At
the same time, the salt is insoluble in CCl4 or hydrocarbons.
In the crystal of [1]2[Te4Cl18], each anion interacts with two cations forming discrete
electroneutral units (Fig. 4) which leads to good solubility of the salt in such common organic
solvents as CHCl3 and CH3CN. In contrast, crystal of poorly soluble [1]2[Te3Cl14] contains
infinite double chains of the anions bound by numerous interactions with four chains of the
cations (Fig. 5).
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There are numerous shortened contacts in the crystal of [4]2[TeCl6]. Every Cl atom have
contacts with Se atoms, the distances are in the range 3.12-3.60 Å (sum of VdW radii is 3.65 Å).
There are no contacts between the anions, but Se…Se contacts between the cations are observed
(Fig. 6; Se…Se distance is 3.67 Å, the sum of VdW radii is 3.80 Å). The octahedral anion
[TeCl6]2– is considerably distorted (Fig. 2).
Figure 4. Shortened contacts (Å) in the ion pairs of [1]2[Te4Cl18] in the crystal.
Figure 5. Shortened contacts in the crystal of [1]2[Te3Cl14].
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
Figure 6. Shortened contacts Se…Se between cations in crystal of [4]2[TeCl6].
Shortened contacts Cl…Cl were observed for crystals of [1][SbCl6], (3.36 Å,[11] sum of VdW
radii is 3.50 Å), [2][SbCl6] (3.35 Å), [3][SbCl6] (3.33 Å), [4][SbCl6] (3.32 Å) and [1]2[Te4Cl18],
(3.30 and 3.43 Å).
A new anion [Te3Cl14]2– in crystals of [1]2[Te3Cl14] consists of three distorted TeCl6
octahedra connected one with another via one or two bridging Cl atoms. Typically for di- and
trinuclear chlorotellurates,[14] the symmetry of [Te3Cl14]2– is far from perfect. Lengths of terminal
bonds Te–Cl lie in the range 2.324-2.484 Å typical of well-known anions [Te2Cl10]2– and
[Te3Cl13]2–. The axial bonds Te–Cl of atom Te1 (Fig. 2) are the longest amongst related terminal
bonds. Lengths of the bridging bonds Te–Cl are quite typical.[14] The atom Cl2B (Fig. 2) forms
both the shortest bond amongst two-coordinated Cl atoms (2.605 Å) and the longest (3.070 Å)
bond in [Te3Cl14]2–. Overall, anion [Te3Cl14]2– can formally be considered as a product of addition
of TeCl4 (atom Te1) to anion [Te2Cl10]2– (atoms Te2 and Te3) at two axial positions (atoms Cl1A
and Cl2B).
A new anion [Te4Cl18]2– in the crystal of salt [1]2[Te4Cl18] has an inversion center. Its
asymmetrical part is more regular than the anion [Te3Cl14]2–. Anion [Te4Cl18]2– could be described
as two [Te2Cl10]2– species bridged via two axial atoms Cl. Lengths of bonds Te–Cl lie in the
range 2.326-2.368 Å for terminal bonds and in the range 2.754-2.899 Å for bridging ones (Fig.
2).
In the molecule of compound 11, Te…O distance of 2.461 Å is much shorter than the sum of
VdW radii of Те and O atoms (3.58 Å). It is only by 0.328 Å larger than length of ordinary
Те(IV)–О covalent bond (2.133 Å).[20] Deviations of other bond lengths of Te–C–C–N=S=O
fragment from typical ones of respective ordinary, aromatic or double bonds do not exceed 0.03
Å. Thus, there is a six-membered heterocycle with one coordination Te–O bond in the compound
11. In the crystal, molecules of 11 form dimers via shortened contacts Te…Cl (or elongated
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
coordination bonds Те–Cl) of 3.379 Å (the sum of VdW radii is 3.81 Å). As a result, atoms Te
possess distorted octahedral configuration (Fig. 7).
Figure 7. Shortened contacts Te…Cl between molecules of 11 in the crystal.
Conclusion
Salts [1][Cl], [2][SbCl6], [3][SbCl6], [4][SbCl6] [1]2[Te3Cl14], [4]2[TeCl6] and [1]2[Te4Cl18] of
sterically-hindered chalcogen-varied Herz cations were synthesized and structurally defined by
XRD to be synthetic precursors of the corresponding Herz radicals (generation and
characterization of the latter will be published elsewhere). Anions [Te3Cl14]2– and [Te4Cl18]2– were
previously unknown.
The synthetic approaches performed well for S and Se containing Herz cations were
unsuccessful in the case of their 1-Te congener. A very different chemistry was observed leading
particularly to the formation of [Te3Cl14]2– and [Te4Cl18]2– together with compound 11 bearing in
the ortho-positions of benzene ring functions –TeCl3 and –N=S=O connected by shortened
intramolecular contact / coordination bond Te…O. On treatment of [1][Cl] with TeO2 in hot
DMF, a chalcogen exchange was not detected by solution 1H NMR.
Thus, synthesis of Te containing Herz cations and subsequently Herz radicals remains a
serious challenge requiring design of original approaches which are not conceptually connected
with S and / or Se chemistry.
Experimental Section
1
13
14
77
General Procedures. H, C, N, Se and 125Te NMR spectra were obtained with a Bruker
DRX-500 spectrometer at frequencies of 500.13 (1H), 125.76 (13C), 95.38 (77Se) MHz for [2][Cl],
[3][Cl], [4][Cl]; Bruker AV-600 spectrometer at frequencies of 600.30 (1H), 150.95 (13C), 43.36
(14N), 114.49 (77Se) and 189.39 (125Te) MHz for [4]2[TeCl6] and 11; and Bruker AV-300
spectrometer at frequencies of 300.13 (1H) and 75.47 (13C) and Bruker AV-400 spectrometer at
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
frequency of 400.13 (1H) for other compounds. The standards were tetramethylsilane (TMS),
ammonia (NH3; liq.), dimethylselenide (Me2Se) and dimethyltelluride (Me2Te). Solutions in
CDCl3 were used unless otherwise indicated.
High-resolution mass-spectra (EI, 70 eV) were taken with Finnigan MAT MS-8200 and DFS
Thermo Electron mass-spectrometers. Elemental analyses were performed with Carlo Erba
Model 1106 instrument (C, H, N, S) and with atomic emission spectrometer Agilent 4100 MP-
AES (Se, Sb). UV-Vis spectra were collected with Hewlett-Packard 8453 spectrophotometer for
CHCl3 solutions.
Crystallographic Analysis. Single-crystal XRD data (Table 2; for isomorphous mixture of [3]
[SbCl6] and [4][SbCl6], see Supporting Information) were obtained with a Bruker P4
diffractometer for [1][Cl] ∙ CHCl3, [2][SbCl6], isomorphous mixture of [3][SbCl6] and [4][SbCl6],
[4]2[TeCl6], [1]2[Te3Cl14] and 11; and with a Bruker Kappa Apex-II diffractometer for [3][SbCl6],
[4][SbCl6] and [1]2[Te4Cl18]; with graphite-monochromated Mo-Kα (0.71073 Å) radiation. The
structures were solved by direct methods using the SHELXS-97 program[21] and refined by the
least-squares method in the full-matrix anisotropic (isotropic for H atoms) approximation using
the SHELXL-97 program.[21] Hydrogen atoms were located geometrically. The obtained
structures were analyzed for shortened contacts between non-bonded atoms using the
PLATON[22] and MERCURY[23] programs. Atomic coordinates, thermal parameters, bond lengths
and bond angles have been deposited at the Cambridge Crystallographic Data Center as CCDC-
1811126 ([1][Cl] ∙ CHCl3), -1811127 ([2][SbCl6]), -1811128 ([3][SbCl6]), -1811129 ([4][SbCl6]),
-1811130 ([4]2[TeCl6]), -1811131 ([1]2[Te3Cl14]), -1811132 ([1]2[Te4Cl18]) and -1811133 (11).
These data can be obtained free of charge from the Center.
Preparations. The syntheses described below were carried out under argon and in absolute
solvents unless otherwise indicated. The reagents were added dropwise and the solvents were
distilled off under reduced pressure.
4,6-Di-tert-butyl-1,2,3-benzothiaselenazolium chloride [2][Cl] and hexachloroantimonate
[2][SbCl6]: а) A mixture of salt [1][Cl][3c,11] (0.64 g, 2.12 mmol), NaOH (1.00 g, 25 mmol) and
96% EtOH (10 mL) was refluxed for 6 h, cooled and diluted with H2O (20 mL). A stream of air
was passed through the reaction mixture for 16 h, and the mixture was extracted with benzene (3
× 10 mL). The extract was washed with water (5 mL), dried with MgSO4 and evaporated. The
residue was recrystallized from EtOH. 2,2’-Diamino-3,3’,5,5’-di-tert-butyldiphenyldisulfide 7[24]
was obtained in the form of yellow needles, 0.14 g (28%).
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
b) A solution of H2O (5.4 mg, 0.3 mmol) in Et2O (1.3 mL) was added to a solution of 7 (140
mg, 0.3 mmol) and PPh3 (91.2 mg, 0.35 mmol) in Et2O (1.5 mL). After 3 h, the mixture was
diluted with CH2Cl2 (1.5 mL) and added to a stirred suspension of SeCl4 (obtained by
chlorination of Se, 48.5 mg, 0.61 mmol) in 3 mL of CH2Cl2. The dark-red solution formed was
evaporated. The residue was dissolved in 0.4 mL of CH2Cl2, then toluene (6 mL) was added and
the solution was poured into 50 mL of hexane. The precipitate was filtered off, washed with 10
mL of hexane and dried in vacuo. Salt [2][Cl] was obtained in the form of orange powder, 185.9
mg (83%), m. p. 120-130 oC. NMR, δ: 1H: 8.44, 7.62, 1.51, 1.37; 13C: 164.8, 163.9, 161.1, 151.5,
126.0, 119.8, 37.7, 36.7, 30.5, 30.0; 77Se: 1468. MS, m/z: 314.0496 M+-Cl (calcd. for
C14H20NS80Se 314.0481). UV-Vis, λ/nm (logε): 410 (4.05), 356 (3.65), 246 (4.01).
c) SbCl5 (0.017 mL, 39.7 mg, 0.13 mmol) was added to a solution of [2][Cl] (46.3 mg, 0.13
mmol) in 0.6 mL of CH2Cl2, then hexane (0.6 mL) was carefully added to form two layers. As
mutual diffusion of the solvents ceased, the solution was removed with a syringe and the solid
was dried in vacuo. Salt [2][SbCl6] was obtained in the form of red crystals, 56.2 mg (65%), m.
o
p. 186-204 C (dec.). Found (%): C 25.99; H 3.09; S 5.28; N 2.20. Calc. for C14H20Cl6NSSbSe
(%): C 25.96; H 3.11; S 4.95; N 2.16.
2-Bromo-4,6-di-tert-butylaniline (9): Conc. HCl (15 mL) was added to a stirred mixture of 2-
bromo-4,6-di-tert-butylnitrobenzene[25] (6.90 g, 22 mmol), Zn powder (4.53 g, 69 mmol) and 5
mL of water over a period of 15 min to avoid vigorous boiling. The reaction mixture was
refluxed for 1 h and a solution of NaOH (30 g, 0.75 mol) in 50 mL of water was added. The
mixture was cooled and extracted with Et2O (4 × 25 mL). The extract was dried with CaCl2,
o
filtered, the solvent was distilled off and the residue was distilled in vacuo, b. p. 140-142 C / 1
Torr. Compound 9[26] was obtained in the form of colourless oil, 4.24 g (68%).
Isomorphous mixtures of chlorides [3][Cl] and [4][Cl] and hexachloroantimonates [3]
o
[SbCl6] and [4][SbCl6]: a) At 20 С, to a stirred solution of compound 9 (852 mg, 3 mmol) in
Et2O (10 mL) 1.98 М solution of n-BuLi in hexane (4.55 mL, 9 mmol) was added over a period
of 5 min. After 10 min a finelly powdered Se (237 mg, 3 mmol) was added to dissolve quickly.
After 10 min, Me3SiCl (1.5 mL, 1.28 g, 12 mmol) was added. After 2 h the solution was refluxed
for 30 min for the coagulation of LiCl. The mixture was cooled, filtered and evaporated. The
residue was dissolved in 1 mL of ССl4 and 1 mL of SOCl2 was added. The mixture was refluxed
for 30 min, cooled and poured into 50 mL of hexane. The solution was decanted from the
precipitate and 10 mL of toluene was added. The crystalline solid was filtered off, washed with
toluene and dried in vacuo. Isomorphous mixture of [3][Cl] and [4][Cl] was obtained in the form
1
77
1
of orange powder, 196 mg. NMR, δ: [3][Cl]: H: 9.42, 7.75, 1.53, 1.39; Se: 1385; [4][Cl]: H:
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
9.14, 7.60, 1.49, 1.38; 77Se: 1492, 1314. The ratio 3:4 was approximately 3:2 according to NMR
77
1Н and Se data. MS, m/z: 3: 314.0483 M+-Cl (calcd. for C14H20NS80Se 314.0481); 4: 361.9913
M+-Cl (calcd. for C14H20N80Se2 361.9926).
b) To a stirred solution of the mixture of [3][Cl] and [4][Cl] (196 mg) in СН2Сl2 (2 mL),
SbCl5 (0.076 mL, 180 mg, 0.6 mmol) was added followed by hexane (10 mL) to form two-layer
system. As mutual diffusion of the solvents ceased, the solution was removed with a syringe and
crystals were dried in vacuo. Isomorpous mixture of [3][SbCl6] and [4][SbCl6] was obtained in
the form of red crystals, 314 mg. According to XRD, the ratio 3:4 was 71:29. Found (%): C
25.40; H 3.01; Cl 32.12; N 2.08; Sb 18.30; Se 15.52. Calc. for C14H20Cl6NS0.71SbSe1.29: C 25.45;
H 3.05; Cl 32.20; N 2.12; Sb 18.43; Se 15.24.
o
4,6-Di-tert-butyl-1,2,3-benzodiselenazolium hexachloroantimonate [4][SbCl6]: At –70 С, to
a stirred solution of compound 9 (462 mg, 1.62 mmol) in Et2O (10 mL) 1.7 М solution of t-BuLi
in pentane (3 mL) was added. After 1 h a finelly powdered Se (151 mg, 1.91 mmol) was added
o
and the mixture was slowly warmed up to 20 С and Me3SiCl (0.9 mL, 770 mg, 7.1 mmol) was
added. After 1 h the solution was filtered and evaporated. The residue was dissolved in CHCl3 (6
mL) and a solution of SeOCl2 prepared by dissolving of SeO2 (208 mg, 1.88 mmol) in Me3SiCl
o
(803 mg, 7.40 mmol)[27] was added. The mixture was refluxed 30 min, cooled to 20 С and
diluted with 50 mL of toluene. After 2 days the mixture was filtered and evaporated. The residue
was dissolved in 10 mL of toluene and a solution of SbCl5 (0.2 mL, 467 mg, 1.56 mmol) in 10
mL of CHCl3 was added. The mixture was evaporated, the residue washed with toluene and
CHCl3. Salt [4][SbCl6] was obtained in the form of dark purple-red powder, 153 mg (14%), dec.
172-207 oC. Found (%): C 24.18; H 2.98; Cl 31.03; N 1.97; Se 22.58. Calc. for C14H20Cl6NSbSe2:
C 24.20; H 2.90; Cl 30.62; N 2.02; Se 22.73. Crystals suitable for XRD were grown from CHCl3
solution by adding of hexane and slow diffusion in the two-layer system formed.
4,6-Di-tert-butyl-1,2,3-benzothiaselenazolium chloride [3][Cl] and hexachloroantimonate
[3][SbCl6]: a) To a solution of [4][SbCl6] (70 mg, 0.1 mmol) in EtOH (96%, 5 mL), KOH (81
mg, 1.45 mmol) and NaBH4 (65 mg, 1.7 mmol) were added and the mixture was gently heated to
~50 oC. Then it was acidifyed with acetic acid to pH = 6 and extracted with СН2Сl2 (4 × 5 mL).
The extract was dried with Na2SO4, filtered and evaporated to dryness. The residue was
dissolved in CCl4 (25 mL), the S2Cl2 (0.1 mL) was added and the mixture was heated to boiling
and then cooled. The orange precipitate was filtered off, washed with CCl4 and dried in vacuo.
Salt [3][Cl] was obtained in the form of orange powder, 27 mg (77%).
b) To a stirred solution of [3][Cl] (27 mg, 0.077 mmol) in СН2Сl2, (2 mL) SbCl5 (0.01 mL,
23 mg, 0.077 mmol) was added followed by hexane (10 mL) form two-layer system. As mutual
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
diffusion of the solvents ceased, the solution was removed with a syringe and crystals were dried
in vacuo. Salt [3][SbCl6] was obtained in the form of red crystals, 44.5 mg (89%), m. p. 190-203
oC (dec.). Found (%): C 25.91; H 3.11; S 5.02; N 2.19; Cl 32.50. Calc. for C14H20Cl6NSSbSe (%):
C 25.96; H 3.11; S 4.95; N 2.16; Cl 32.84.
Attempted preparation of 4,6-di-tert-butyl-2,1,3-benzothiatellurazolium (5) and 4,6-di-tert-
butyl-2,1,3-benzoselenatellurazolium (6). Salts [1]2[Te3Cl14], [1]2[Te4Cl18] and [4]2[TeCl6],
o
and N-sulfinyl-2-amino-3,5-di-tert-butylphenyltellurium trichlorid (11): At –70 С, to a
stirred solution of compound 9 (462 mg, 1.62 mmol) in of Et2O (10 mL) 1.7 М solution of t-
BuLi in pentane (3 mL) was added. After 1 h a finelly powdered Te (236 mg, 1.85 mmol) was
o
added, the mixture was slowly warmed to 20 С and Me3SiCl (0.9 mL, 770 mg, 7.1 mmol) was
added. After 1.5 h the solution was filtered and evaporated. The residue was dissolved in 5 mL
of hexane, filtered and evaporated, and the residue was treated as follows:
a) The residue was dissolved in 4 mL of ССl4 and SOCl2 (0.8 mL, 1.33 g, 11.1 mmol) was
carefully added to give a light precipitate. The reaction mixture was refluxed until the precipitate
dissolution (~15 min). The solution was cooled and hexane (12 mL) was added to form two
layers. After a day, a dark tar precipitated. The solution was decanted, diluted with hexane (15
o
mL), filtered and concentrated in vacuo to the beginning of crystallization. After 1 day at 0 C,
the crystals were filtered off, washed with hexane and dried in vacuo. Compound 11 was
o
obtained in the form of yellow-orange crystals, 288 mg (37%), m. p. 230-231 C (dec.). Found
(%): C 34.93; H 4.22; Cl 22.10; N 3.05; S 6.31. Calc. for C14H20Cl3NOSTe: C 34.72; H 4.16; Cl
1
21.96; N 2.89; S 6.62. NMR, δ: H: 8.67, 7.68, 1.50, 1.40; 13C: 158.8, 148.7, 145.6, 135.8, 131.1,
14
127.8, 37.5, 36.8, 30.9, 30.7; N: 327; 125Te: 1336. The tar was extracted with boiling ССl4 and
the insoluble orange powder was filtered off, dissolved in CH2Cl2 and precipitated with hexane at
the conditions of slow diffusion. Salt [1]2[Te4Cl18] was obtained in the form of orange needles,
1
13
13 mg (0.9%). NMR, δ: H: 8.73, 8.00, 1.65, 1.50; C (CD3CN): 166.1, 162.9, 161.3, 151.7,
130.0, 119.2, 38.6, 38.3, 30.7, 30.5; 125Te (CD3CN): 1470.
b) The residue was dissolved in 15 mL of 1,2-dichloroethane and a solution of S2Cl2 (0.68
mL, 1.10 g, 8.2 mmol) in 15 mL of 1,2-dichloroethane was added over a period of 30 min. After
2 h, the mixture was refluxed for 2 h, cooled and filtered. The filter was washed with 5 mL of
1,2-dichloroethane, then hexane (75 mL) was added to the filtrate to form two layers. As mutual
diffusion of the solvents ceased, the solution was removed with a syringe and the wool-like
orange residue was dried in vacuo. Then it was dissolved in CHCl3, the solution was filtered,
insoluble matter was washed with CHCl3 on the filter and the filtrate was distilled off to give
yellow-orange crystals, 614 mg. The insoluble in CHCl3 product was dried in vacuo to give a
1
13
mixture of yellow and red crystals, 131 mg. Н and С (CD3CN) NMR spectra of these two
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
products were very similar one to another and to the spectra of [1][Cl] suggesting that the
products are likely mixtures of salts of cation 1 with various anions. On slow evaporation of the
solution in CDCl3, [1]2[Te3Cl14] (2.7 mg) precipitated in the form of orange crystals suitable for
XRD.
c) The residue dissolved in 4 mL of 1,2-dimethoxyethane was added to a stirred solution of
SeCl4 (prepared by chlorination of 128 mg, 1.62 mmol of Se) in 5 mL of the same solvent. After
4 h, the precipitate formed was filtered off, washed with Et2O and dried in vacuo. Salt
[4]2[TeCl6] was obtained in the form of red powder, 272 mg (32%)%), m. p. 230-235 oC (dec.).
1
13
NMR, δ: H: 9.05, 7.65, 1.52, 1.43; C: 171.9, 169.8, 161.2, 152.2, 126.8, 125.3, 38.5, 37.6,
77
30.7, 30.1; Se: 1504, 1312; 125Te: 1430. Found (%): Cl 18.71. Calcd for C28H40Cl6N2Se4Te: Cl
20.05 Low Cl content is likely due to admixture of [4][Cl] salt (calcd for C14H20ClNSe2 Cl
8.96%).
o
2,2’-Diamino-3,3’,5,5’-di-tert-butyldiphenylditelluride (12): At –70 С, 1.6 М solution of
t-BuLi in pentane (10 mL) was added to a stirred solution of compound 9 (1.5 g, 5.28 mmol) in
Et2O (30 mL). After 1 h, a finelly powdered Te (676 mg, 5.28 mmol) was added and reaction
o
mixture was slowly warmed to 20 С. Then the mixture was shaken with a solution of NH4Cl
(856 mg, 16 mmol) and K3[Fe(CN)6] (1.74 g, 5.28 mmol) in water (40 mL). The organic layer
was separated and the aqueous phase was extracted with Et2O (2 × 15 mL). Organic solutions
were combined, dried with CaCl2, evaporated and the residue was recrystallized from hexane.
o
Compound 12 was obtained in the form of black crystals, 1.05 g (60%), m. p. 172-173 C. NMR,
1
δ: H: 7.74, 7.24, 4.36, 1.40, 1.24; 125Te: 223. MS, m/z: 664.1595 (calcd. 664.1594 for
C28H44N2126Te130Te and 664.1589 for C28H44N2128Te2).
Attempted chalcogen exchange in [1][Cl]: A mixture of [1][Cl] (302 mg, 1 mmol), TeO2 (1.6
o
g, 10 mmol) and DMF (7 mL) was stirred for 8 h at 120 C. Then it was cooled to ambient
temperature, filtered, the light-gray (i.e. displayed no sign of Herz salts) solid was washed with
1
CH2Cl2 (10 mL) and the filtrate was evaporated to dryness in vacuo. The H NMR spectrum of
the residue dissolved in CDCl3 revealed no signals in the range 7.5-10.0 ppm characteristic of
1,2,3-benzodichalogenazoliums.
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
Table 2. XRD data for compounds [1][Cl] ∙ CHCl3, [2][SbCl6], [3][SbCl6], [4][SbCl6],
[4]2[TeCl6], [1]2[Te3Cl14], [1]2[Te4Cl18] and 11.
Compound
[1][Cl] ∙CHCl3
[2][SbCl6]
[3][SbCl6]
Empirical formula
C14H20NS2 + CHCl3
Cl-
+
C14 H20 NSSe + SbCl6
C14H20NSSe + SbCl6
Formula weight
421.25
647.78
647.78
Temperature K
153(2)
153(2)
200(2)
Wavelength Å
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/c
Crystal system
Space group
Unit cell dimensions a Å
6.0695(7)
18.869(2)
18.2401(19)
90
12.509(3)
15.326(3)
12.497(2)
90
12.5272(7)
15.1855(7)
12.4328(5)
90
b Å
c Å
α o
β o
90.695(6)
90
102.388(15)
90
101.416(2)
90
γ o
Volume Å3
2088.8(4)
4
2339.9(8)
4
2318.3(2)
4
Z
Density (calcd.) Mg.m–3
Abs. coefficient mm–1
F(000)
1.340
1.839
1.856
0.762
3.508
3.541
872
1256
1256
Crystal size mm3
Θ range for data collection °
Index ranges
0.12 × 0.20 × 0.40
2.2–27.0
0.24 × 0.38 × 0.90
2.1–28.0
0.04 × 0.08 × 0.80
1.7–27.5
–7 ≤ h ≤ 0, 0 ≤ k ≤ 24, – 0 ≤ h ≤16, –20 ≤ k ≤0, – –16 ≤ h ≤ 16, –19 ≤ k ≤
23 ≤ l ≤ 23
16≤ l ≤16
19, –15 ≤ l ≤ 16
Reflections collected
4997
5844
40876
Independent reflections
Completeness to θ %
4569 R(int) = 0.044
100.0
5603 R(int )= 0.039
99.1
5334 R(int )= 0.046
99.9
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices I > 2σ(I)
4569 / 0 / 199
1.06
5603 / 6 / 245
1.07
5334/ 0 / 223
1.03
R1 = 0.0684, wR2
0.1561
=
=
R1 = 0.0484, wR2
0.1319
=
=
R1 = 0.0284, wR2
0.0844
=
=
Final R indices (all data)
R1 = 0.1395, wR2
0.1867
R1 = 0.0564, wR2
0.1383
R1 = 0.0365, wR2
0.0973
Largest diff. peak / hole e.Å–3 0.67 / –0.62
1.19 / –1.55
1.27 / –1.27
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
Table 2 (continued)
Compound
[4][SbCl6]
C14H20NSe2 + SbCl6
694.68
[4]2[TeCl6]
C14H20NSe2 + ½(TeCl6)
530.38
[1]2[Te3Cl14]
2(C14H20NS2) + Te3Cl14
1411.96
Empirical formula
Formula weight
Temperature K
Wavelength Å
Crystal system
Space group
200(2)
173(2)
200(2)
0.71073
0.71073
0.71073
Monoclinic
P21/c
Triclinic
Monoclinic
P21/n
P-1
Unit cell dimensions a Å 12.5773(5)
11.0783(6)
13.3850(9)
13.8085(9)
94.734(2)
104.863(2)
98.757(2)
1940.1(2)
4
18.275(6)
9.7693(3)
29.2844(8)
90
b Å
15.2280(6)
12.3780(4)
90
c Å
α o
β o
100.963(1)
90
103.924(1)
90
γ o
Volume Å3
2327.46(15)
4
5055.9(4)
4
Z
Density (calcd.) Mg.m–3
Abs. coefficient mm–1
F(000)
1.982
1.816
1.855
5.001
4.954
2.649
1328
1024
2720
Crystal size mm3
0.06 × 0.2 × 0.6
0.20 × 0.30 × 0.30
3.1–29.1
0.02 × 0.05 × 0.30
3.0–27.5
Θ
range
for
data 1.7–32.9
collection °
Index ranges
–18 ≤ h ≤ 17, –22 ≤ k ≤ –15 ≤ h ≤ 14, –17 ≤ k ≤
–23 ≤ h ≤ 22, –12 ≤ k ≤
12, –38 ≤ l ≤ 33
50054
22, –16 ≤ l ≤ 18
54123
17, –17 ≤ l ≤ 18
37194
Reflections collected
Independent reflections
Completeness to θ %
7975 R(int) = 0.048
99.9
10036 R(int) = 0.069
99.8
11578 R(int) = 0.054
99.9
Data
/
restraints
/
7975 / 0 / 222
10036 / 13 / 378
2696 / 0 / 217
parameters
Goodness-of-fit on F2
1.03
1.02
1.07
Final R indices I > 2σ(I)
R1
0.0867
=
0.0346, wR2
0.0529, wR2
=
=
R1 = 0.0556, wR2 =
0.1345
R1
0.1281
=
0.0674, wR2
=
=
Final R indices (all data)
R1
0.1070
=
R1 = 0.0898, wR2 =
0.1552
R1
0.1372
= 0.1113, wR2
Largest diff. peak / hole 1.81 / –2.05
e.Å–3
4.03 / –3.72
0.84 / –1.95
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
Table 2 (continued)
Compound
[1]2[Te4Cl18]
11
Empirical formula
C14H20NS2 + ½(Te4Cl18)
C14H20NOSTeCl3
Formula weight
Temperature K
Wavelength Å
Crystal system
Space group
840.68
296(2)
0.71073
Triclinic
P-1
484.32
150(2)
0.71073
Orthorhombic
Pbca
Unit cell dimensions a Å 10.2355(5)
16.8937(8)
11.6920(7)
19.211(1)
90
b Å
10.2877(4)
14.8907(6)
77.662(2)
79.120(2)
68.496(1)
1414.6(1)
2
c Å
α o
β o
90
γ o
90
Volume Å3
3794.6(4)
8
Z
Density (calcd.) Mg.m–3
Abs. coefficient mm–1
F(000)
1.974
1.696
3.065
2.098
800
1904
Crystal size mm3
0.04 × 0.12 × 0.90
0.10 × 0.50 × 0.50
2.1–30.1
Θ
range
for
data 3.5–27.5
collection °
Index ranges
–13 ≤ h ≤ 13, –12 ≤ k ≤ –23 ≤ h ≤ 18, –16 ≤ k ≤
13, –19 ≤ l ≤ 18
15048
15, –25 ≤ l ≤ 27
21711
Reflections collected
Independent reflections
Completeness to θ %
6337 R(int) = 0.028
99.4
5506 R(int) = 0.028
98.9
Data
/
restraints
/
6337 / 0 / 259
5506 / 0 / 190
parameters
Goodness-of-fit on F2
1.02
1.06
Final R indices I > 2σ(I)
R1
0.0588
=
0.0262, wR2
0.0364, wR2
=
=
R1 = 0.0266, wR2
0.0691
=
=
Final R indices (all data)
R1
0.0633
=
R1 = 0.0335, wR2
0.0853
Largest diff. peak / hole 0.63 / –0.46
e.Å–3
1.75 / –0.56
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10.1002/ejic.201701470
European Journal of Inorganic Chemistry
Acknowledgements
A. Y. M., I. Y. B. and Y. M. V. are grateful to the Russian Foundation for Basic Research
(project 15-03-08970), and I. Y. B. and A. V. Z. to the Russian Foundation for Basic Research
(project 17-53-12057) and Deutsche Forshungsgemeineschaft (project BE 3716/6-1), for
financial support. The authors thank the Multi-Access Center Chemical Service, Siberian Branch
of the Russian Academy of Sciences, for instrumental facilities.
Keywords: Chalcogen-nitrogen heterocycles · Chlorotellurate anions · Herz salts · Selenium ·
Tellurium
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Entry for the Table of Contents
FULL PAPER
Salts of sterically-hindered 1,2,3-
Chalcogen-nitrogen chemistry
benzodithiazolium
and
its
Se
Alexander Yu. Makarov,* Irina Yu.
Bagryanskaya, Yulia M. Volkova,
Makhmut M. Shakirov, and Andrey V.
Zibarev*
congeners with anions [Cl]– and
[SbCl6]–
structurally defined.
were
synthesized
and
The same
methods applied to synthesis of their
Te analogs unexpectedly gave salts of
Te-free cations with anions [TeCl6]2–,
[Te3Cl14]2– and [Te4Cl18]2– and neutral
acyclic compound bearing groups
TeCl3 and N=S=O in ortho-positions of
benzene ring.
Page No. – Page No.
Salts
Chalcogen-Varied
of
Sterically-Hindered
Herz Cations
Including Those with New Anions
[Te3Cl14]2– and [Te4Cl18]2–
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