Formation and crystal structure of 2, 3, 5-triphenyltetrazolium hexachlorophosphate and dichlorophosphate(V), [TPT]+[PCl6]-and [TPT]+[PO2Cl2

Article abstract of DOI:10.1515/znb-2009-0901

2,3,5-Triphenyltetrazolium hexachlorophosphate, [C₁₉H ₁₅N₄]+[PCl₆[TPT]+[PCl₆]" (1), and 2, 3, 5-triphenyltetrazolium dichlorophosphate(V), [C₁₉H ₁₅N₄]+[PO₂C

Full text of DOI:10.1515/znb-2009-0901

Formation and Crystal Structure of 2,3,5-Triphenyltetrazolium
Hexachlorophosphate and Dichlorophosphate(V), [TPT]+[PCl6]–
and [TPT]+[PO2Cl2]–
Tao Xie, Wolfgang Brockner, and Mimoza Gjikaj
Institut fu¨r Anorganische und Analytische Chemie der TU Clausthal, Paul-Ernst-Str. 4,
38678 Clausthal-Zellerfeld, Germany
Reprint requests to PD Dr. Mimoza Gjikaj. Fax: (+49)5323 722995.
E-mail: mimoza.gjikaj@tu-clausthal.de
Z. Naturforsch. 2009, 64b, 989 – 994; received June 25, 2009
2,3,5-Triphenyltetrazolium hexachlorophosphate, [C19H15N4]+[PCl6]−, [TPT]+[PCl6]− (1), and
2,3,5-triphenyltetrazolium dichlorophosphate(V), [C19H15N4]+[PO2Cl2]−, [TPT]+[PO2Cl2]− (2),
were synthesized by reactions of anhydrous 2,3,5-triphenyltetrazolium chloride, [TPT]+Cl−, and
2,3,5-triphenyltetrazolium chloride monohydrate [TPT]+Cl− · H2O, with PCl5 in dry acetonitrile,
and their crystal structures were determined by single-crystal X-ray diffraction analysis. In the title
compounds, the [TPT]+ cations show a face-to-face stacked orientation between the phenyl rings of
neighboring molecules, which is caused by intermolecular π ···π interactions. The crystal structure of
compound 1 consists of layers of 2,3,5-triphenyltetrazolium cations and hexachlorophosphate anions.
In compound 2 the tetrahedral [PO2Cl2]− anions exhibit approximate C2v symmetry with P–O bond
˚
˚
lengths from 1.454 to 1.463 A and P–Cl bond lengths from 2.038 to 2.050 A. The Raman spectrum
of compound 1 was recorded, and the assignment of the [PCl6]− Raman modes is proposed.
Key words: 2,3,5-Triphenyltetrazolium Hexachlorophosphate(V), 2,3,5-Triphenyltetrazolium
Dichlorophosphate(V), [PCl6]−, [PO2Cl2]−, Crystal Structure, Raman Spectroscopy
Introduction
chloride ion donor among the alkali chlorides, is able
to form the unique Cs+[PCl6]− [10]. Furthermore
and until now, hexachlorophosphates are only known
with large polyatomic cations as, e. g., [Ph4P]+ [11],
[N(PCl3)2]+ [12, 13], and [P(NPCl3)4]+ [14].
2,3,5-Triphenyltetrazolium chloride, TTC (a com-
mercial product), and other tetrazolium salts are
mainly used as color indicators for the determination
of reduction equivalents in diagnostic applications as
well as in clinical research and cell biology [1]. Other-
wise, TTC acts as an excellent chloride ion donor for
Lewis acidic metal chlorides as, e. g., SbCl5, CdCl2,
CoCl2, or CuCl2 leading to the respective chlorometal-
lates [2 – 5]. With other anions also stable compounds
as for example [TPT]+[ReO4]− (triphenyltetrazolium
perrhenate), or solvates like TTC · H2O (triphenyltetra-
zolium chloride hydrate), are formed [1, 6]. TTC might
also be used for studies of salt syntheses where the size
of the cationic group is related to the kind and structure
of the corresponding anionic units.
Usually, phosphorus pentachloride behaves as
strong chloride ion donor giving [PCl4]+ as an in-
dicative unit in vibrational spectroscopic investigations
[7 – 9]. On the other hand, the examples of phospho-
rus pentachloride acting as chloride ion acceptor re-
sulting in [PCl6]− are scarce. Only CsCl, the strongest
Otherwise, general structural informations of di-
chlorophosphates(V) are scarce, too. From vibrational
spectra it has been concluded that [PO2Cl2]− acts
mainly as a bridging unit in main group and tran-
sition metal compounds [15 – 18]. The complete vi-
brational spectrum of [(CH3)4Sb] [PO2Cl2] is known
allowing the conclusion that it is built up ioni-
cally [19], as well as its homolog [(CH3)4As]+
[PO2Cl2]− [20], referenced in [19]. The first X-ray
crystal structure determination of the [PO2Cl2]− an-
ion in 2-chloro-1,3-diisopropyl-4,5-dimethyl-imidaz-
olium dichlorophosphate(V) was published 2002 by
Kuhn et al. [21]. Furthermore, the crystal struc-
ture of cyclohexyl tert-butyl ammonium dichloro-
phosphate(V) was published recently [22]. The for-
tuitous encounter of single crystals of the title com-
pound 2 now gave the opportunity to determine its
structure.
c
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T. Xie et al. · 2,3,5-Triphenyltetrazolium Hexachlorophosphate and Dichlorophosphate(V)
˚
Table 1. Crystal and structure refinement data of
Table 2. Interatomic distances (A) and angles (deg) for the
[TPT]+[PCl6]− (1) and [TPT]+[PO2Cl2]− (2).
[TPT]+ cation in 1 and 2 with estimated standard deviations
in parentheses.
Formula
C19H15Cl6N4P
543.02
C19H15Cl2N4O2P
433.22
Mr, g mol−1
Crystal size, mm3
Crystal system
Space group
Compound 1
0.29×0.27×0.26 0.28×0.25×0.24
N(1)–N(5)
N(1)–N(2)
N(2)–N(3)
N(1)–C(6)
1.312(3)
1.341(3)
1.305(3)
1.449(3)
N(3)–C(4)
N(5)–C(4)
N(2)–C(12)
C(4)–C(18)
1.448(3)
1.349(4)
1.448(3)
1.460(4)
triclinic
monoclinic
P21/n
15.791(3)
16.124(2)
17.476(2)
90
114.70(1)
90
4042.4(9)
8
1.42
0.4
1776
223(2)
¯
P1
˚
a, A
9.288(2)
10.291(2)
13.959(3)
87.05(1)
78.75(1)
63.38(1)
1168.9(3)
2
1.54
0.8
548
223(2)
˚
b, A
N(2)–N(1)–N(5)
N(2)–N(1)–C(6)
N(5)–N(1)–C(6)
N(1)–N(2)–N(3)
N(3)–N(2)–C(12)
110.2(2)
124.3(2)
125.5(2)
110.1(2)
126.7(2)
N(1)–N(2)–C(12)
N(2)–N(3)–C(4)
N(1)–N(5)–C(4)
N(3)–C(4)–N(5)
N(3)–C(4)–C(18)
123.2(2)
103.8(2)
103.4(2)
112.4(2)
123.9(3)
˚
c, A
α, deg
β, deg
γ, deg
3
˚
V, A
Z
Compound 2
Dcalc, g cm−3
µ (MoKα ), mm−1
F(000), e
T, K
N(1)–N(5)
N(1)–N(2)
N(2)–N(3)
N(1)–C(6)
N(3)–C(4)
N(5)–C(4)
1.309(3)
1.328(3)
1.314(2)
1.444(3)
1.333(3)
1.347(3)
N(24)–N(28)
N(24)–N(25)
N(25)–N(26)
N(24)–C(29)
N(26)–C(27)
N(26)–C(27)
1.314(2)
1.326(3)
1.315(3)
1.447(3)
1.345(3)
1.333(3)
2θ range, deg
1.00 – 25.68
−11 ≤ h ≤ 11,
−12 ≤ k ≤ 12,
−15 ≤ l ≤ 17
1.00 – 25.00
−18 ≤ h ≤ 18,
−18 ≤ k ≤ 18,
−20 ≤ l ≤ 20
17783 / 6745
0.0565
hkl ranges
N(2)–N(1)–N(5)
N(2)–N(1)–C(6)
N(5)–N(1)–C(6)
N(1)–N(2)–N(3)
N(3)–N(2)–C(12)
N(1)–N(2)–C(12)
N(2)–N(3)–C(4)
N(1)–N(5)–C(4)
N(3)–C(4)–N(5)
109.9(2)
126.2(2)
123.8(2)
110.3(2)
122.9(2)
126.8(2)
103.6(2)
103.7(2)
112.5(2)
N(25)–N(24)–N(28)
N(28)–N(24)–N(29)
N(25)–N(24)–C(29)
N(26)–N(25)–C(24)
N(26)–N(25)–C(35)
N(24)–N(25)–C(35)
N(25)–N(26)–C(27)
N(24)–N(28)–C(27)
N(24)–N(28)–C(27)
110.0(2)
123.5(2)
126.4(2)
110.2(2)
124.2(2)
125.6(2)
103.3(2)
103.8(2)
112.7(2)
Refl. measured / unique 18955 / 4394
Rint
0.0487
Param. refined
R1 [I ≥ 2σ(I)]a
wR2 [I ≥ 2σ(I)]a
R1 (all data)a
wR2 (all data)a
Parameters A / B
(weighting scheme)b
GoF (F2)c
331
0.0406
0.0790
0.0652
0.0869
0.0352 / 0.3339
625
0.0435
0.0963
0.0516
0.1011
0.0437 / 2.8713
1.059
0.34 / −0.29
1.045
0.75 / −0.63
Crystal and molecular structures
−3
˚
∆ρfin (max/min), e A
R1 = ΣꢀFo| − |Fcꢀ/Σ|Fo|, wR2 = [Σw(Fo − Fc2)2/Σw(Fo2)2]1/2
;
a
2
2,3,5-Triphenyltetrazolium hexachlorophosphate,
b w = [σ2(Fo2) + (AP)2 + BP]−1, where P = (Max(Fo2, 0) + 2Fc2)/3;
[TPT]+[PCl6]− (1)
GoF = [Σw(Fo −Fc2)2/(nobs −nparam)]1/2
.
c
2
[TPT]+[PCl6]− crystallizes in the triclinic space
group P1 (no. 2) with two formula units in the unit cell
(Table 1). The crystal structure of compound 1 con-
¯
Results and Discussion
Direct treatment of anhydrous 2,3,5-triphenyltetraz- sists of layers of 2,3,5-triphenyltetrazoliumcations and
olium chloride, [TPT]+Cl−, or 2,3,5-triphenyltetraz- hexachlorophosphate anions. The closest interaction
olium chloride monohydrate, [TPT]+Cl− · H2O, with contact C(10)···Cl–PCl5 (3.389 A) is slightly shorter
˚
PCl5 in dry acetonitrile provided the colorless crys- than the analogous closest contact taken from the crys-
+
−
˚
talline solids of compounds 1 and 2, respectively. The tal structure of [TPT] [SbCl6] (3.538 A) [2] (Fig. 1).
products are extremely sensitive to air and moisture, However, in both cases, the contacts are close to the
but can be stored safely under an atmosphere of dry ni- van der Waals distance, and the interactions appear to
trogen.
be largely of a Coulomb type. No hydrogen bonds are
The [TPT]+ cation is common to both salts. This found.
presents an opportunity to compare its structure in dif-
The packing diagram of compound 1 shows the
ferent compounds. The C–N and N–N bond lengths in face-to-face stacked orientation between the phenyl
the tetrazolium ring do not vary significantly between rings of neighboring molecules, which is caused
both structures (Table 2). Comparison with other crys- by intermolecular π ···π interactions (Fig. 2). The
tal structures of 2,3,5-triphenyltetrazoliumsalts reveals closest contact between the neighboring phenyl
that the internal dimensions of the [TPT]+ cation are rings is 3.68 A, which is in excellent agreement
˚
largely insensitive to the local environment [2, 23].
with the values determined for the simplest pro-
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991
Fig. 2. Face-to-face stacking of the
phenyl rings in crystals of compound 1.
˚
Table 3. Selected interatomic distances (A) and angles (deg)
for [TPT]+[PCl6]− (1) and [TPT]+[PO2Cl2]− (2).
Compound 1
P–Cl(1)
P–Cl(2)
P–Cl(3)
2.114(1)
2.118(1)
2.122(1)
P–Cl(4)
P–Cl(5)
P–Cl(6)
2.140(1)
2.161(1)
2.182(1)
Cl(1)–P–Cl(2)
Cl(1)–P–Cl(3)
Cl(2)–P–Cl(3)
Cl(1)–P–Cl(4)
Cl(2)–P–Cl(4)
Cl(3)–P–Cl(4)
Cl(1)–P–Cl(5)
91.19(5)
91.18(5)
91.70(5)
178.00(5)
90.17(5)
90.26(5)
89.44(5)
Cl(2)–P–Cl(5)
Cl(3)–P–Cl(5)
Cl(4)–P–Cl(5)
Cl(1)–P–Cl(6)
Cl(2)–P–Cl(6)
Cl(3)–P–Cl(6)
Cl(4)–P–Cl(6)
177.63(5)
90.58(4)
89.15(4)
89.40(5)
90.13(5)
178.07(5)
89.13(5)
Compound 2
P(1)–O(1)
P(1)–O(2)
P(1)–Cl(1)
P(1)–Cl(2)
1.454(2)
1.463(2)
2.038(1)
2.050(1)
P(2)–O(3)
P(2)–O(4)
P(2)–Cl(3)
P(2)–Cl(4)
1.456(2)
1.463(2)
2.046(1)
2.050(1)
O(1)–P(1)–O(2)
O(1)–P(1)–Cl(1)
O(1)–P(1)–Cl(2)
O(2)–P(1)–Cl(1)
O(2)–P(1)–Cl(2)
Cl(1)–P(1)–Cl(2)
124.27(8)
107.51(9)
108.56(9)
108.05(9)
105.89(8)
99.89(5)
O(3)–P(2)–O(4)
O(3)–P(2)–Cl(3)
O(3)–P(2)–Cl(4)
O(4)–P(2)–Cl(3)
O(4)–P(2)–Cl(4)
Cl(3)–P(2)–Cl(4)
123.97(9)
108.57(9)
106.66(8)
107.11(8)
107.81(8)
100.19(5)
Fig. 1. Perspective view of the [TPT]+ cation and the
[PCl6]− anion in compound 1.
totype of π ···π interactions, the benzene dimer
[24, 25].
The five atoms in the tetrazolium ring [N(1), N(2),
N(3), C(4) and N(5)] are coplanar. N(1)–N(5) and
˚
P–Clax and P–Cleq bond lengths are 2.127 and 2.146 A
(Table 3). These data correspond very well with those
found in [NP2Cl6]+[PCl6]− and [N(PCl3)2]+[PCl6]−
[13].
˚
N(2)–N(3) are almost equivalent (1.305 and 1.312 A)
˚
(Table 2). The N(1)–N(2) bond (1.341 A) is longer than
the former two bonds. This may be ascribed to the re-
pulsion between the relevant phenyl groups. The tor-
sion angles of the phenyl rings are 116.00, 117.83 and
176.27◦. These values agree well with those reported
for {[TPT]+}2[CdCl4]2− [26], [TPT]+[CoCl2(NPh=
N–CPh=N–NPh]− [27] and [TPT]+[SbCl6]− [2].
The anionic unit is placed in an approximately oc-
tahedral Oh symmetry with cis-Cl−P–Cl angles all
within a 1.19◦ deviation from 90◦, and trans-Cl−P–
Cl angles of 177.6 and 178.1◦ in the equatorial posi-
2,3,5-Triphenyltetrazolium dichlorophosphate,
[TPT]+[PO2Cl2]− (2)
Title compound 2 crystallizes in the monoclinic
space group P21/n (no. 14) with eight formula units
per unit cell. The asymmetric unit of the structure con-
tains two independent [TPT]+ cations and [PO2Cl2]−
anions (Table 1).
The phosphorus atoms P(1) and P(2) have slightly
tions, and 178.0◦ in the axial positions. The average distorted tetrahedral coordination, with P–O bond
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T. Xie et al. · 2,3,5-Triphenyltetrazolium Hexachlorophosphate and Dichlorophosphate(V)
Table 4. Raman frequencies (cm−1) of crystalline [TPT]+
[PCl6]− (1) below 500 cm−1 along with their estimated in-
tensities and proposed assignmenta.
[TPT]+[PCl6]−
Raman
[PCl6]−
Assignment / Oh
in crystalline [PCl4]+[PCl6]− b mode description
354 vvs
360
444
283
ν1 / A1g : νs
ν3 / F1u : νas
ν2 / Eg : ν
Fig. 3. Face-to-face stacking of the phenyl rings forming
compound 2. (Hydrogen atoms have been omitted for clar-
ity).
270 sh / 262 m
240 sh
238
ν5 / F2g : δ
285
ν4 / F1u : δ
[ν6 / F2u : (i. a.)]?
Lattice vibration
[168]c
100 sh, 81 vs
a
Estimated intensities: s: strong, m: medium, w: weak, v: very,
b
c
sh: shoulder. ν: stretching, δ: bending; ref. [31]; estimated
value [32].
Footnote 1. Raman (cm−1 / intensity) of crystalline [TPT]+-
[PCl6]−: 3098 vw, 3072 s, 3048 sh, 1607 vvs, 1585 s, 1526 vs, 1487
m, 1454 s, 1415 w, 1372 s, 1329 w, 1225 w-m, 1160 w, 1077 w, 1026
w, 1003 vs, 679 w, 618 vw, 405 vw, 354 vvs, 270 sh, 240 sh, 100 sh,
81 vs.
Fig. 4. Cl···Cl interactions in the crystal structure of
[TPT]+[PO2Cl2]− (2).
˚
lengths from 1.454 to 1.463 A (Table 3), in agreement
˚
Fig. 5. FT-Raman spectrum (λexc. = 1064 nm) of crystalline
[TPT]+[PCl6]− (1). Insert: [PCl6]−-relevant frequency re-
gion below 450 cm−1. (Raman intensity in arbitrary units).
with a normal double bond length (1.45 A) [28]. The
˚
P–Cl bond lengths range from 2.038 to 2.050(1) A. The
bond angles around P(1) range from 99.9 to 124.3◦.
The minimum and maximum values of angles are ob-
served for Cl(1)–P(1)–Cl(2) and O(1)–P(1)–O(2), re-
spectively. For P(2), bond angles are in the region
of 100.2– 124.4◦, with the smallest angle Cl(3)–P(2)–
Cl(4) and the largest O(3)–P(2)–O(4) (Table 3).
Raman spectrum of [TPT] [PCl6] and band assign-
ment for 2,3,5-triphenyltetrazolium hexachlorophos-
phate, [TPT]+[PCl6]− (1)
Compound 1 does consist of [TPT]+ cations and
There is a π ···π stacking interaction between par- [PCl6]− anions. Both units can be clearly detected
allel aromatic phenyl rings, as shown in Fig. 3. The by Raman spectroscopy (Fig. 5). In this contribution
interplanar distance of the phenyl ligands is 3.799 A, the vibrational behavior of [PCl6]− is the more in-
˚
again close to the values found for the benzene dimer teresting part, therefore the Raman spectrum of crys-
[24, 25].
talline [TPT]+[PCl6]− is considered only in the rele-
vant range below 500 cm−1
The vibrational frequencies of the [PCl6]− unit of
.
The chlorine atoms of the [PO2Cl2]− ions play an
important role in the packing of the tetrahedral units,
˚
with a Cl(2)···Cl(3) distance of 3.769 A. This value in- 1 are presented in Table 4 along with the proposed as-
dicates slight van der Waals attraction [29, 30] (Fig. 4). signments and in comparison to literature data [31, 32].
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T. Xie et al. · 2,3,5-Triphenyltetrazolium Hexachlorophosphate and Dichlorophosphate(V)
993
The [TPT]+ frequencies are very similar to those of 2,3,5-Triphenyltetrazolium hexachlorophosphate (1)
[TPT]+Cl− [33] and [TPT]+[SbCl6]− [2], and they are
only given in footnote 1 below Table 4.
A vibrational analysis for the octahedral [PCl6]−
unit delivers [31]:
Anhydrous 2,3,5-triphenyltetrazolium chloride (TTC)
was synthesized according to the literature [34]. A mix-
ture of 335 mg (1 mmol) TTC (dried for 2 h at 120 C)
◦
and of 208.5 mg (1 mmol) PCl5 was g◦ently heated un-
til a homogenous melt was formed (150 C, 10 min). Af-
ter cooling to r. t. 10 mL of dry CH3CN was added giv-
ing a clear solution on warming up. After one week color-
less single crystals (0.293 mg) of the title compound grew
in the solution. The melting temperature was found to be
Γ ([PCl6]−/Oh) = A1g (RE) + E (RE)
vib
g
+ 2 F1u (IR) + F2g (RE) + F2u (i. a.),
with RE = Raman, IR = Infrared and i. a. = inactive,
and with A1g + Eg + F1u as stretching and F1u + F2g as
bending modes.
◦
150 – 152 C. Yield: 54 %. C19H15Cl6N4P (543.04): calcd.
C 42.02, H 2.78, N 10.32; found C 41.68, H 2.97, N 10.01.
The assignment given for the [PCl6]− modes of 1
is made in analogy to the measured [PCl6]− frequen-
cies of solid phosphorus pentachloride consisting of
[PCl4]+[PCl6]− ions (c. f. Table 4). The vibrational fre-
quencies of [PCl6]− are all consistent with the octa-
hedral structure and in agreement with other experi-
mental values [10, 12, 32]. The strongest Raman band
at 354 cm−1 belongs to ν1 / A1g, the medium Raman
mode at 262 cm−1 to ν2 / Eg and the one at 240 cm−1
to ν5 / F2g. The modes below 100 cm−1 are ascribed to
lattice vibrations.
2,3,5-Triphenyltetrazolium dichlorophosphate(V) (2)
A mixture of 352.5 mg (1 mmol) TTC · H2O and of
208.5 mg PCl5 (1 mmol) was gently heated until a homo-
geneous melt was formed. After cooling to r. t. 10 mL of
dry CH3CN was added giving a clear solution on warming
up. After several days colorless crystals (112 mg) of the ti-
tle compound were fo◦rmed. The melting temperature was
found to be 170 – 175 C. Yield: 25.6 %. C19H15Cl2N4O2P
(433.22): calcd. C 52.68, H 3.49, N 12.93; found C 52.31,
H 3.67, N 12.57.
The formation of [PO2Cl2]− in this preparation of
[TPT]+[PCl6]− is due to the presence of water in the reac-
tion mixture (c. f. ref. [6]). Formation of [PO2Cl2]− respec-
tive [TPT]+[PO2Cl2]− is possible by partial hydrolysis of
PCl5 via POCl3 and its primary hydrolysis product HPO2Cl2
[35] in the presence of Cl− according to: PCl5 + 2 H2O +
[TPT]+[Cl]− = [TPT]+[PO2Cl2]− + 4 HCl.
Concluding Remarks
A further member in the very exclusive group of
salt-like dichlorophosphates(V) could be obtained and
structurally characterized. [TPT]+[PO2Cl2]− exhibits
a combination of interactions, namely ionic combined
with weak π-π stacking interactions between parallel
packed phenyl rings of the [TPT] cations. Compound
2 is soluble in CH3CN, and it could be used for the
preparation of further unknown dichlorophosphates(V)
by salt metathesis reactions, as e. g. for the synthesis of
alkali compounds MIPO2Cl2.
X-Ray crystallography
Suitable single crystals of the title compounds were se-
lected under oil protection with the help of a polariza-
tion microscope and transferred to 0.3 mm quartz capil-
laries. The X-ray reflection data were collected on a Stoe-
II single-crystal X-ray diffractometer with MoKα radiation
˚
(λ = 0.71073 A) at a temperature of 223 K. Structure so-
Experimental Section
lution and refinements were carried out by Direct Methods
using the programs SHELXS-97 and SHELXL-97 [36]. All
non-H atom positions were refined anisotropically. Hydrogen
atom positions were determined by final Difference Fourier
Synthesis. Details of crystal data and structure refinement pa-
rameters are summarized in Table 1. For producing the struc-
ture drawings the programs DIAMOND [37] and POV-RAY
[38] were used.
Materials and methods
All manipulations and chemical reactions were performed
in a dry argon atmosphere using standard Schlenk, vacuum-
line and glove-box techniques. Phosphorus pentachloride
(p. a. ≥ 98.0 %, Fluka) and 2,3,5-triphenyltetrazolium chlo-
ride (p. a. ≥ 99.0 %, Fluka) were used without additional pu-
rification. CH3CN was distilled and dried over P4O10. The
melting temperatures were determined on a Bu¨chi 520 appa-
CCDC 734856 (1), and CCDC 734857 (2) contain the
ratus, and the given temperatures are uncorrected values. The supplementary crystallographic data for this paper. These
FT-Raman spectrum of the solid compound 1 was recorded data can be obtained free of charge from The Cambridge
with a Raman module FRA 106 (Nd:YAG laser, 1064 nm) Crystallographic Data Centre via www.ccdc.cam.ac.uk/data
attached to a Bruker IFS 66v interferometer.
request/cif.
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994
T. Xie et al. · 2,3,5-Triphenyltetrazolium Hexachlorophosphate and Dichlorophosphate(V)
Acknowledgements
The authors are indebted to Prof. Dr. Arnold Adam for his
support. We thank K. Bode for recording the Raman spectra
and Dr. V. Zapol’skii for the determination of the melting
points of compounds 1 and 2.
[22] K. Gholivand, M. Pourayoubi, Z. Kristallogr. NCS,
2004, 219, 314.
[23] M. Gjikaj, T. Xie, W. Brockner, Z. Anorg. Allg. Chem.
2009, 635, in press.
[1] M. Predota, V. Petricek, Z. Zak, T. Glowiak, J. Novotny,
Acta Crystallogr. 1991, C47, 738.
[2] M. Gjikaj, T. Xie, W. Brockner, Z. Anorg. Allg. Chem.
2009, 635, 1036.
[24] S. Tsuzuki, K. Honda, T. Uchimaru, M. Mikami,
K. Tanabe, J. Am. Chem. Soc. 2002, 124, 104.
[25] M. O. Sinnokrot, E. F. Valeev, C. D. Sherrill, J. Am.
Chem. Soc. 2002, 124, 10887.
[26] Sh.-F. Zhang, X.-G. Yang, Zh. Liu, W.-H. Li, B.-R.
Hou, Acta Crystallogr. 2007, E63, m1583.
[27] Y. Kawamura, J. Yamauchi, N. Azuma, Acta Crystal-
logr. 1997, B53, 451.
[28] D. E. C. Corbridge, Phosphorus, an outline of it’s
Chemistry, Biochemistry and Technology, (5th Edi-
tion), Elsevier, Amsterdam, 1995.
[29] P. P. K. Claire, G. R. Willey, J. Chem. Soc., Dalton
Trans. 1989, 57.
[3] S.-F. Zhang, X.-G. Yang, Z. Liu, W.-H. Li, B.-R. Hou,
Acta Crystallogr. 2007, E63, m1583.
[4] N. A. Frolova, S. Z. Vatsadze, A. I. Stash, R. D. Rakhi-
nov, N. V. Zyk, Chem. Heterocyclic Compd. 2006, 42,
1444.
[5] Y. Kawamura, J. Yamauchi, N. Azuma, Acta Crystal-
logr. 1997, B53, 451.
[6] D. G. Golovanov, D. S. Perekalin, A. A. Yakovenko,
M. Yu. Antipin, K. A. Lyssenko, Mendeleev Commun.
2005, 15, 237.
[7] F. W. Poulsen, J. Raman Spectrosc. 1981, 11, 302.
[8] A. F. Demiray, W. Brockner, Spectrochim. Acta 1979,
35A, 659.
[30] J. Danielsen, S. E. Rasmussen, Acta Chem. Scand.
1963, 17, 1971.
[31] J. Weidlein, U. Mu¨ller, K. Dehnicke, Schwingungs-
spektroskopie, Thieme Stuttgart, 1982, pp. 140.
[32] H. Siebert, Anwendungen der Schwingungsspektro-
skopie in der Anorganischen Chemie, Springer, Berlin,
1966, pp. 82.
[9] A. F. Demiray, W. Brockner, B. N. Cyvin, S. J. Cyvin, Z.
Naturforsch. 1979, 34a, 362.
[10] A. S. Muir, Polyhedron, 1991, 10, 2217.
[11] H. Gruber, U. Mu¨ller, Z. Kristallogr. NCS 1998, 213,
546.
[12] R. Faggiani, R. J. Gillespie, J. F. Sawyer, J. D. Tyrer,
Acta Crystallogr. 1980, B36, 1014.
[33] Sigma-Aldrich: htpp://www.sigmaaldrich.com/catalog
/search/ProductDetail/Fluka/93140.
[34] H. V. Pechmann, P. Runge, Ber. Deutsch. Chem. Ges.
1894, 27, 2920.
[13] F. Belaj, Acta Crystallogr. 1998, C54, 1735.
[14] F. Belaj, Acta Crystallogr. 1997, B53, 923.
[15] H. Mu¨ller, K. Dehnicke, Z. Anorg. Allg. Chem. 1967,
350, 231.
[35] H. Grunze, Z. Anorg. Allg. Chem. 1961, 313, 316.
[36] G. M. Sheldrick, SHELXS/L-97, Programs for Crys-
tal Structure Determination, University of Go¨ttingen,
Go¨ttingen (Germany) 1997.
[37] K. Brandenburg, DIAMOND (version 3.0), Crystal and
Molecular Structure Visualization, Crystal Impact –
K. Brandenburg & H. Putz GbR, Bonn (Germany)
2004.
[16] K. Dehnicke, A.-F. Shihada, Structure and Bonding
1976, 28, 51.
[17] A. Saavedra, K. Dehnicke, Z. Anorg. Allg. Chem. 1977,
435, 82.
[18] H.-D. Do¨rner, K. Dehnicke, D. Fenske, Z. Anorg. Allg.
Chem. 1982, 486, 136.
[19] B. Eberwein, J. Weidlein, Z. Anorg. Allg. Chem. 1976,
420, 229.
[38] POV-RAY (version 3.5), Trademark of Persistence
of Vision Raytracer Pty. Ltd., Williamstown, Victoria
(Australia); Copyright Hallam Oaks Pty. Ltd., 1994 –
2004.
[20] R. Ott, Dissertation, University of Stuttgart, Stuttgart,
1975.
[21] N. Kuhn, A. Abu-Rayyan, M. Stro¨bele, Z. Anorg. Allg.
Chem. 2002, 628, 2251.
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