Tetraphenylantimony perrhenate and tetraphenylantimony chlorate: Syntheses and structures

Article abstract of DOI:10.1134/S0036023609030103

The reaction of tetraphenylantimony chloride with sodium perrhenate or potassium chlorate yields tetraphenylantimony perrhenate (I) and tetraphenylantimony chlorate (II), respectively. Complex I was also synthesized from pentaphenylantimony and triphenyla

Full text of DOI:10.1134/S0036023609030103

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2009, Vol. 54, No. 3, pp. 389–395. © Pleiades Publishing, Inc., 2009.
Original Russian Text © V.V. Sharutin, V.S. Senchurin, O.A. Fastovets, A.P. Pakusina, O.K. Sharutina, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 3,
pp. 436–442.
COORDINATION
COMPOUNDS
Tetraphenylantimony Perrhenate and Tetraphenylantimony
Chlorate: Syntheses and Structures
V. V. Sharutina, V. S. Senchurina, O. A. Fastovetsb, A. P. Pakusinab, and O. K. Sharutinaa
a Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
b Far East State Agrarian University, Blagoveshchensk, Russia
Received December 26, 2007
Abstract—The reaction of tetraphenylantimony chloride with sodium perrhenate or potassium chlorate yields
tetraphenylantimony perrhenate (I) and tetraphenylantimony chlorate (II), respectively. Complex I was also
synthesized from pentaphenylantimony and triphenylantimony diperrhenate in toluene. According to X-ray dif-
fraction, crystals I and II consist of almost regular tetrahedral tetraphenylstibonium cations (CSbC, 109.4(2)°–
109.5(7)° in I and 109.1(1)°–109.6(1)° in II) and [ReO4]– (OreO, 107.6(3)°–113.3(5)°) and [ClO3]– (OClO,
96.3(9)°, 116.4(5)°) anions, respectively. The average Sb–C bond lengths (2.094(3) Å in I, 2.097(2) Å in II) are
close to the sum of the covalent radii of the Sb and C atoms. The average distances Re–O in complex I
(1.672(4) Å) and Cl–O in complex II (1.315 Å) correspond to multiple bonds.
DOI: 10.1134/S0036023609030103
It is known that pentavalent antimony compounds parameters of molecules of tetraphenylantimony
hydrogen phthalate [23], hydrogen maleinate [20], and
nitrate [24] with the polar covalent Sb–O bond have
similar values, although it is known that the dissocia-
tion constants of the corresponding acids differ
strongly.
The purpose of this work is to synthesize tetraphe-
nylantimony perrhenate (I), and tetraphenylantimony
chlorate (II) and to determine their structures.
with the general formula Ph4SbX (X = Cl, Br, NO3,
OSO2R, OAr, OC(O)R, ONCRR', RC(O)CHC(O)R')
can be synthesized by the substitution reaction from tet-
raphenylantimony halide and alkali metal salts, or from
pentaphenylantimony and an acid HX, or by the ligand
redistribution reaction from pentaphenylantimony and
symmetric antimony derivatives Ph3SbX2 [1–7]. In
compounds of this type, the coordination of the anti-
mony atoms changes from an almost regular tetrahe-
dron [8–10] to an octahedron [11–15], passing through
the trigonal-bipyramidal state [16–22]. It should be
noted that the residues of inorganic and organic OH-
acids are more often prone to the formation of covalent
polar bonds with the antimony atom. The tetrahedral
coordination of the antimony atom is observed in ionic
molecules. The contribution of the ionic component to
the character of the Sb–X bond is determined by the
nature of the X ligand, in particular, by its ability to
delocalize the negative charge. In the case of efficient
delocalization, the stable X– anion and [Ph4Sb]+ cation
are formed, and the bond in Ph4Sbï is ionic. Tetraphe-
nylantimony perchlorate [8], hydrogen sulfate [9], and
2,5-dimethylbenzenesulfonate [10] can serve as exam-
ples of the compounds with the ionic bond. The relative
arrangement of the cation and anion in crystals of these
compounds and the distortion of their configuration
compared to the ideal one are determined by the influ-
ence of the factors that provide the minimum of the
crystal lattice energy as a whole. It is not always possi-
ble to estimate beforehand the contribution of the ionic
component to the character of the Sb–X bond, because
the use of the äa value of the corresponding acid is
EXPERIMENTAL
Synthesis of complex I. (a) A mixture of pentaphe-
nylantimony (0.50 g, 0.99 mmol), triphenylantimony
diperrhenate (0.65 g, 0.99 mmol), and benzene (20 mL)
was heated in a glass evacuated ampule for 1 h at 90°ë.
The solvent was removed. The residue was recrystal-
lized from a benzene–hexane (3 : 1) mixture. Colorless
crystals of compound I with mp = 298°ë (decomp.)
were obtained (0.90 g, 78%). IR (cm–1): 3062 m,
3031 w, 1650 w, 1573 w, 1478 vs, 1433 vs, 1388 m,
1338 vs, 1309 s, 1162 s, 1065 vs, 1019 s, 994 vs,
924 vs, 906 vs, 853 m, 739 vs, 690 vs, 610 m, 452 vs,
434 vs.
For C24H20O4ReSb, anal. calcd. (%): C, 42.35;
H, 2.94.
Found (%): C, 41.84; H, 2.54.
(b) A solution of sodium perrhenate (0.58 g,
2.15 mmol) in water (10 mL) was added to a solution of
tetraphenylantimony chloride (1.00 g, 2.15 mmol) in
water (20 mL). The precipitate formed was dried and
recrystallized from acetone. Colorless crystals of com-
pound I with Tm = 298°ë (decomp.) were obtained in
incorrect for this estimate. For instance, the geometric 68% yield (1.00 g).
389

390
SHARUTIN et al.
Table 1. Crystallographic data and details of the X-ray experiment and refinement for structures I and II
Value
Characteristic
I
II
FW
680.35
100(2)
513.60
295(2)
T, K
Crystal system
Tetragonal
Tetragonal
Space group
I4
I4
a, Å
c, Å
V, Å3
Z
12.8306(3)
12.5675(3)
6.5938(2)
6.8006(2)
1085.50(5)
1074.10(5)
2
2
ρ
µ
calcd, g/cm3
Mo, mm–1
2.082
6.843
1.588
1.431
F(000)
644
512
Shape (crystal size, mm)
θ, deg
Prism (0.15 × 0.20 × 0.15)
3.18 – 29.92
Prism (0.78 × 0.24 × 0.24)
2.29 – 37.51
Index ranges
–17 ≤ h ≤ 17,
–17 ≤ k ≤ 17,
–9 ≤ l ≤ 9
–21 ≤ h ≤ 19,
–19 ≤ k ≤ 21,
–5 ≤ l ≤ 11
All reflections
5647
1484 (Rint = 0.0210)
1291
6640
2642 (Rint = 0.0190)
2299
Independent reflections;
Reflections with I > 2σ(I)
Number of refined parameters
GOOF
68
68
0.781
1.111
R factors for F2 > 2σ (F2)
R factors for all reflections
Extinction coefficient
R1 = 0.0150, wR2 = 0.0359
R1 = 0.0153, wR2 = 0.0360
Not determined
–0.814/0.896
R1 = 0.0271, wR2 = 0.0641
R1 = 0.0607, wR2 = 0.0953
0.00012(8)
Residual electron density (min/max), e/Å3
–0.555/1.096
Synthesis of complex II. A mixture of tetraphenyl-
X-ray crystallographic analysis of compounds I
antimony chloride (1.00 g, 2.15 mmol) and potassium and II was carried out from single crystals with natural
chloride (0.30 g, 2.45 mmol) in water (20 mL) was kept faceting on Bruker AXS Smart Apex and Bruker-Non-
for 24 h at 12°ë. The solvent was removed. Transparent ius X8Apex diffractometers, respectively. The struc-
needle-like crystals with Tm = 228°ë (decomp.) were tures were solved by direct methods and refined by the
least-squares method in the anisotropic approximation
for non-hydrogen atoms. The positions of the hydrogen
atoms were calculated geometrically and included in
the refinement as riding on their bonded atoms. The
data were collected and edited and the unit cell param-
eters were refined using the SADABS [25], SMART,
and SAINT Plus [26] programs. All calculations for
structure determination and refinement were performed
with the SHELXTL/PC program package [27].
obtained by recrystallization from acetone (0.98 g,
89%). IR (cm–1): 3055 m, 2641 w, 2332 w, 2135 m,
2087 m, 1966 m, 1890 m, 1817 m, 1769 w, 1729 w,
1653 m, 1572 s, 1480 vs, 1436 vs, 1335 vs, 1303 s,
1190 s, 1070 s, 965 s, 845 vs, 736 vs, 688 vs, 596 vs,
451 s, 435 vs.
For C24H20ClO3Sb anal. calcd. (%): C, 56.14;
H, 3.89.
Selected crystallographic data and results for the
Found (%): C, 55.84; H, 3.21.
refinement of structures I and II are presented in
The IR spectra of compounds I and II were Table 1. The coordinates and temperature factors of
recorded on an FSM 1201 FT-IR spectrophotometer as atoms are given in Table 2. Selected bond lengths and
KBr pellets.
bond angles are listed in Table 3.
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TETRAPHENYLANTIMONY PERRHENATE AND TETRAPHENYLANTIMONY CHLORATE
391
Table 2. Atomic coordinates of atoms (×104) and isotropic Table 3. Selected bond lengths (d) and bond angles (ω) in
equivalent temperature parameters (×103) in structures I and II
structures I and II
Atom
x
y
z
Ueq, Å2
Bond
d, Å
Angle
ω, deg
I
I
Sb(1)
Re(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
O(1)
5000
0
7500
13(1)
20(1)
18(1)
23(1)
29(1)
29(1)
25(1)
20(1)
Sb(1)–C(1)
Re(1)–O(1)
2.094(3) C(1)#1Sb(1)C(1)
1.672(4) C(1)#2SbC(1)
O(1)Re(1)O(1)#3
1.392(4) O(1)Re(1)O(1)#4
1.394(4)
109.52(7)
109.38(15)
107.6(3)
5000
–5000
5000
5780(2)
6565(2)
7066(3)
6769(3)
5982(3)
5489(2)
5027(5)
–1080(2)
–737(3)
–1452(3)
–2491(3)
–2827(2)
–2126(2)
–3911(5)
II
9336(4)
10630(4)
11874(5)
11857(5)
10561(5)
9277(5)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
113.3(5)
1.389(4)
1.387(4)
6393(10) 123(2)
Symmetry codes: #1) –x + 1/2, y + 1/2, –z + 3/2; #2) –x + 1, –y, z; #3)
x – 1, –y, –z + 1; #4) –x + 1, –y – 1, z.
Sb(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
Cl(1)
0
0
0 29.14(5)
II
0.07609(16) –0.11264(15) 0.1787(3) 34.1(3)
0.04347(19) –0.21785(19) 0.1777(4) 45.5(4)
Sb(1)–C(1)
Cl(1)–O(1)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
2.097(2) C(1)#1Sb(1)C(1)
1.315(6) C(1)#2Sb(1)C(1)
1.384(3) O(1)Cl(1)O(1)#3
1.388(3) O(1)Cl(1)O(1)#4
1.388(4)
109.64(5)
109.13(10)
116.4(5)
96.3(9)
0.0905(3)
0.1693(3)
0.2039(3)
0.1570(3)
0.0000
–0.2891(2)
–0.2552(3)
–0.1522(3)
–0.0785(2)
0.5000
0.3070(5) 60.4(7)
0.4315(5) 66.3(9)
0.4282(5) 69.5(10)
0.3024(4) 53.8(6)
0.7500
102.0(8)
1.371(6)
O(1)* –0.0768(7)
0.5132(8)
0.6210(12) 205(5)
Symmetry codes: #1) –x, y, –z; #2) –x, –y, z; #3) –x + 1/2, y – 1/2,
–z + 3/2; #4) –x, –y + 1, z.
* The site occupancy factor is 0.75.
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SHARUTIN et al.
O(1c)
C(1b)
Sb(1)
C(1a)
O(1a)
O(1)
Re(1)
C(1)
C(1c)
O(1b)
Fig. 1. Structures of the cation and anion in compound I.
RESULTS AND DISCUSSION
The cation geometry in complexes I and II is similar to
that found in tetraphenylantimony perchlorate (III)
(CSbC 109.44(8)° and 109.49(8)°, Sb–C 2.095(2) Å [8]).
Complexes I and II are uncolored crystalline sub-
stances that are stable in air and soluble in aromatic
hydrocarbons and polar organic solvents. They were
synthesized from tetraphenylantimony chloride and the
corresponding sodium or potassium salts
In the [ReO4]– anion of structure I, the rhenium atom
has the expected insignificantly distorted tetrahedral
coordination (the OReO angles are 107.6(3)° and
113.3(5)°). The Re–O distance (1.672(4) Å) corre-
sponds to a multiple bond. In tetramethylantimony per-
rhenate (IV), the OReO angles vary in a range of
Ph4SbCl + NaReO4
Ph4SbCl + KClO3
[Ph4Sb][ReO4],
[Ph4Sb][ClO3].
The reactions occur in an aqueous solution almost 106.73(3)°–111.13(5)°, and the Re–O bond lengths are
instantly.
1.710(4)–1.755(4) Å [28]. Crystal I contains short con-
tacts between the hydrogen atoms in the ortho position
of the phenyl substituent and the oxygen atoms of the
perrhenate anion (é(1)···ç(6Ä) 2.38 Å), as well as the
ë···ç contacts between the hydrogen and carbon atoms
in the meta positions of the phenyl substituents of the
adjacent cations (ë(5)···ç(3Ä) 2.86 Å). Crystal IV also
exhibits many intermolecular hydrogen bonds é···ç–ë
(é···ç 2.39–2.53 Å). In addition, the antimony atom in
the [Me4Sb]+ cation of structure IV is sterically unhin-
dered, which allows this atom to contact with three
anions (Sb···O 3.094, 3.135, and 3.153 Å, whereas the
sum of the van der Waals radii of Sb and O is 3.70 Å
[29]). Each anion has three short contacts é···Sb. Evi-
dently, the listed intermolecular interactions result in an
elongation of the Re–O bonds in compound IV com-
Tetraphenylantimony perrhenate (I) was also syn-
thesized by the ligand redistribution reaction from pen-
taphenylantimony and tetraphenylantimony diperrhen-
ate:
Ph5Sb + Ph3Sb(ReO4)2
2[Ph4Sb][ReO4].
The reaction mixture in a benzene solution should
be heated (90°ë, 1 h) for the reaction to be completed.
According to the X-ray diffraction data, complexes I
and II have ionic structures. The antimony atoms in the
tetraphenylantimony cations of compounds I (Fig. 1)
and II (Fig. 2) have an almost undistorted tetrahedral
coordination. The CSbC angles are 109.4(2)° and
109.5(7)° in complex I and 109.1(1)° and 109.6(1)° in
complex II, whereas the Sb–C bond lengths are
2.094(3) Å in complex I and 2.097(2) Å in complex II. pared to similar bonds in compound I and in a notice-
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TETRAPHENYLANTIMONY PERRHENATE AND TETRAPHENYLANTIMONY CHLORATE
393
C(4)
C(3)
C(5)
C(2)
C(6)
O(1c)
C(6e)
C(1)
C(5e)
C(4e)
Sb(1)
C(1e)
C(1f)
Cl(1)
C(6d)
C(1d)
C(5d)
O(1b)
C(3e)
O(1a)
C(2d)
C(2e)
O(1)
C(3d)
C(4d)
C(3f)
C(4f)
C(6f)
C(5f)
Fig. 2. Structures of the cation and anion in compound II.
able distortion of the SbC4 tetrahedron in the cation of
structure IV.
It is known that the chlorate anion [ClO3]– has the
structure of a trigonal pyramid, where the Cl–O bond
length ranges from 1.452 to 1.507 Å and the OClO
angle is 106° [30]. The [ClO3]– anion in structure II was
found to be disordered over four equiprobably occupied
positions of the oxygen atoms (75% each, the chlorine
atom being in the special position). The OClO angles
are 96.3(9)° and 116.4(5)°, and the Cl–O distance
(1.315(6) Å) corresponds to a multiple chlorine–oxy-
gen bond. In the [ClO4]– perchlorate anion of complex
III, the OClO angles are 108.6(4)° and 111.3(2)°, and
the Cl–O bond (1.361(5) Å), as should be expected, is
longer than that in complex II.
Crystals II and IV are isostructural. The unit cell is
body-centered: the cations are arranged at the vertices
and in the center of the tetragonal cell, and the anions
are located at the rectangular faces A and B with the
antimony and chlorine atoms in special positions (sym-
metry S4) (Fig. 3). In crystal I, the [ReO4]– anions are
arranged in the center and at the vertices of the unit cell,
and the cations occupy positions at the faces of the cell
(Fig. 4).
Fig. 3. Packing of the cations and anions in the crystal struc-
ture of complex II (projection along the c axis).
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394
SHARUTIN et al.
Fig. 4. Packing of the cations and anions in the crystal structure of complex I (projection along the c axis).
8. G. Ferguson, C. Glidewell, D. Lloyd, and S. Metcalfe,
J. Chem. Soc., Perkin Trans. II, 731 (1988).
ACKNOWLEDGMENTS
We are grateful to G.K. Fukin (Razuvaev Institute of
Organometallic Chemistry, Russian Academy of Sci-
ences, Nizhni Novgorod) for the X-ray diffraction anal-
ysis of complex I and to E.V. Peresypkina (Institute of
Inorganic Chemistry, Siberian Branch, Russian Acad-
emy of Sciences, Novosibirsk) for the X-ray diffraction
analysis of complex II.
9. V. V. Sharutin, A. P. Pakusina, I. V. Egorova, et al., Zh.
Obshch. Khim. 73 (4), 569 (2003).
10. V. V. Sharutin, O. K. Sharutina, L. P. Panova, and
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12. V. V. Sharutin, O. K. Sharutina, O. P. Zadachina, et al.,
Koord. Khim. 29 (1), 8 (2003).
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