Tetra- and triarylantimony fluorobenzoates: Synthesis and structures

Article abstract of DOI:10.1023/A:1015517216693

The reactions of pentaarylantimony (Ar₅Sb, where Ar = Ph or p-Tol) with triarylantimony bis(pentafluorobenzoate) and triarylantimony bis(3,4,5-trifluorobenzoate) in toluene afforded tetraarylantimony pentafluoro- and 3,4,5-trifluorobenzoates in up to 90% yields. The starting triarylantimony bis(pentafluorobenzoates) and bis(3,4,5-trifluorobenzoates) were prepared in ether by oxidative addition involving triarylstibine, hydrogen peroxide, and pentafluorobenzoic or 3,4,5-trifluorobenzoic acid, respectively, in up to 98% yields. Tetra-p-tolylantimony pentafluorobenzoate and triphenylantimony bis(pentafluorobenzoate) were structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid with axial carboxy groups. In these compounds, the Sb atoms and carbonyl O atoms are linked by intramolecular contacts, which are especially pronounced in the latter complex (the Sb...O(=C) distances are 3.377(3) and 2.943(2), 3.167(2) A, respectively).

Full text of DOI:10.1023/A:1015517216693

Russian Journal of Coordination Chemistry, Vol. 28, No. 5, 2002, pp. 333–340. Translated from Koordinatsionnaya Khimiya, Vol. 28, No. 5, 2002, pp. 356–363.
Original Russian Text Copyright © 2002 by Sharutin, Sharutina, Bondar’, Pakusina, Gatilov, Adonin, Starichenko.
Tetra- and Triarylantimony Fluorobenzoates:
Synthesis and Structures
V. V. Sharutin, O. K. Sharutina, E. A. Bondar’, A. P. Pakusina, Yu. V. Gatilov,
N. Yu. Adonin, and V. F. Starichenko
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
Vorozhtsov Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
Received March 15, 2001
Abstract—The reactions of pentaarylantimony (Ar5Sb, where Ar = Ph or p-Tol) with triarylantimony bis(pen-
tafluorobenzoate) and triarylantimony bis(3,4,5-trifluorobenzoate) in toluene afforded tetraarylantimony pen-
tafluoro- and 3,4,5-trifluorobenzoates in up to 90% yields. The starting triarylantimony bis(pentafluoroben-
zoates) and bis(3,4,5-trifluorobenzoates) were prepared in ether by oxidative addition involving triarylstibine,
hydrogen peroxide, and pentafluorobenzoic or 3,4,5-trifluorobenzoic acid, respectively, in up to 98% yields.
Tetra-p-tolylantimony pentafluorobenzoate and triphenylantimony bis(pentafluorobenzoate) were structurally
characterized by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal
bipyramid with axial carboxy groups. In these compounds, the Sb atoms and carbonyl O atoms are linked by
intramolecular contacts, which are especially pronounced in the latter complex (the Sb···O(=C) distances are
3.377(3) and 2.943(2), 3.167(2) Å, respectively).
Pentaphenylantimony Ar5Sb is known to react
with triphenylantimony diacylates
EXPERIMENTAL
The starting acylates Ar3Sb(OC(O)Ar')2 were pre-
pared following the Thepe method [4] using oxidative
addition in ether at T = 20°ë for 12 h.
Ar3Sb[OC(O)Ar']2 to give tetraphenylantimony acy-
lates Ar4SbOC(O)Ar' [1–3]. It was shown that the
presence of functional groups in the aryl ring of an
acylate substituent sometimes prevents the above
redistribution of aryl radicals. Thus, the reaction of
triphenylantimony disalicylate with pentaphenylan-
timony does not yield tetraphenylantimony salicylate
[2]. To elucidate the factors that determine the
behavior of these reagents, we studied the reactions
of Ar5Sb (I) (Ar = C6H5 or C6H4CH3-4) with triaryl-
antimony diacylates Ar3Sb[OC(O)Ar']2 (II) (Ar' =
C6F5, or C6H2F3-3,4,5) and examined the molecular
and crystal structures of triphenylantimony bis(pen-
tafluorobenzoate) and tetra-p-tolylantimony pen-
tafluorobenzoate.
Triphenylantimony bis(pentafluorobenzoate) (IIa).
Pentafluorobenzoic acid (1.35 g, 6.37 mmol) and 30%
aqueous hydrogen peroxide (3.17 mmol, 0.36 ml) were
added to a solution of triphenylstibine (1.12 g, 3.17 mmol)
in 10 ml of ether. The reaction mixture was kept at 20°ë
for 12 h. The crystals formed were filtered off and dried.
IR (ν, cm–1): 1672 vs, 1340 vs, 1260 vs, 1100 s,
1065 m, 990 vs, 920 s.
Other triarylantimony dibenzoates (IIb)–(IId) were
obtained analogously. Elemental analysis data are
given in Table 1.
The compounds Ar4SbOC(O)Ar' (III) were syn-
thesized in a solution of an arene (90°C, 1 h) by the
reaction
Ar5Sb + Ar3Sb[OC(O)Ar']2
2Ar4SbOC(O)Ar'
(III)
(I)
(II)
(Ar = (a, c) C6H5 and (b, d) 4-CH3C6H4 and Ar' = (a, b) C6F5 and (c, d) 3,4,5-F3C6H2).
Tetraphenylantimony
(IIIa). A mixture of pentaphenylantimony (0.91 g,
1.79 mmol) and triphenylantimony bis(pentafluoroben-
zoate) (1.40 g, 1.80 mmol) was kept in 15 ml of toluene 1060 m, 980 vs.
pentafluorobenzoate at 90°ë for one hour. The solvent was removed, and the
residue was recrystallized from toluene–heptane (1 : 1).
IR (ν, cm–1): 1655 vs, 1335 vs, 1275 vs, 1098 s,
1070-3284/02/2805-0333$27.00 © 2002 åÄIä “Nauka /Interperiodica”

334
SHARUTIN et al.
Table 1. Yields, melting points, and elemental analysis data for tetra- and triarylantimony pentafluorobenzoates and 3,4,5-
trifluorobenzoates
Content (found/calculated), %
Complex
Empirical formula
Yield, %
Tmp, °C
C
H
F
IIa
C32H15SbO4F10
C35H21SbO4F10
C32H19SbO4F6
C35H25SbO4F6
C31H20SbO2F5
C35H28SbO2F5
C31H22SbO2F3
C35H30SbO2F3
50.13/49.55
51.11/51.41
54.19/54.62
56.12/56.38
57.83/58.03
60.06/60.26
61.06/61.49
63.48/63.54
1.65/1.93
2.75/2.57
2.83/2.70
3.49/3.36
3.47/3.12
3.84/4.02
3.87/3.64
4.87/4.54
24.22/24.52
23.02/23.26
16.08/16.22
15.14/15.30
14.43/14.82
13.29/13.63
9.05/9.42
97
98
99
99
69
78
97
96
173
147
236
171
161
150
161
173
IIb
IIc
IId
IIIa
IIIb
IIIc
IIId
8.34/8.62
The IR spectrum and melting point of compound
Atomic coordinates and thermal parameters are
IIIa are identical to those of the substance synthesized given in Table 2. The bond lengths and angles are listed
from pentaphenylantimony and fluorobenzoic acid in [5]. in Table 3.
Other tetraarylantimony benzoates (IIIb)–(IIId)
were obtained analogously (Table 1).
RESULTS AND DISCUSSION
The aforementioned syntheses of tetraarylantimony
fluorobenzoates showed that the presence of F atoms in
the aryl ring of the benzoato ligand does not change the
mechanism of radical redistribution in reaction (1)
between pentaarylantimony and symmetrical arylanti-
mony derivatives. Therefore, the area of application of
this reaction proves to be wider than was previously
assumed [7].
IR spectra were recorded on a Hitachi-215 spec-
trometer (suspension in Vaseline oil between NaCl
plates).
X-ray diffraction analysis of crystals IIa and IIIb
was carried out on a Bruker P4 automated diffractome-
ter (graphite monochromator, MoKα radiation, θ/2θ
scan mode).
The X-ray diffraction analysis of triphenylantimony
bis(pentafluorobenzoate) (IIa) revealed a distorted tri-
gonal-bipyramidal coordination of the Sb atom with
axial carboxy O atoms (Fig. 1). The sum of the CSbC
angles in the equatorial plane is 359.9°, and the Sb–O
distances (2.122(2) and 2.154(2) Å) are close to analo-
gous distances in other triphenylantimony diacylates
[8]. Note that the Sb–O (2.137 and 2.127 Å) and Sb–C
bond lengths (2.094–2.120 Å) in triphenylantimony
dibenzoate (IIe) [9] are virtually the same as in IIa.
The crystals of IIa are triclinic: at 20°ë a =
12.1218(5) Å, b = 12.1640(5) Å, c = 12.7307(5) Å, α =
71.369(3)°, β = 62.988(3)°, γ = 60.461(3)°, V =
1443.9(1) Å3, space group P1 , ρcalcd = 1.783 g/cm3,
crystal size 0.5 × 0.3 × 0.2 mm, µåÓ = 1.059 mm–1, 2θ <
50°, and Z = 2. The final residuals are wR2 = 0.0798 and
R = 0.0349, S = 1.026 for all 6717 reflections and wR2 =
0.0772 and R = 0.0303 for 6055 reflections with F >
4σ(F).
The presence of the carboxy groups in tri- and tet-
raarylantimony acylates suggests an intramolecular
interaction of the Sb atom with the carbonyl O atom
(i.e., the CN of antimony can increase to 7 and 6,
respectively) [9, 10]. In complex IIa, the Sb···O(=C)
intramolecular contacts are 2.943(2) and 3.167(2) Å;
they are substantially longer than those in IIe (2.699
and 2.813 Å) (the sum of the van der Waals radii of anti-
mony and oxygen equals 3.70 Å [11]). The Sb···O(=C)
The crystals of IIIb are monoclinic: at 20°ë
a = 11.3947(5) Å, b = 15.7868(6) Å, c = 17.6219(5) Å,
β = 103.813(3)°, V = 3078.3(2) Å3, space group P21/n,
ρcalcd = 1.505 g/cm3, crystal size 0.56 × 0.45 × 0.42 mm,
µMo = 0.957 mm–1, 2θ < 50°, and Z = 4. The final resid-
uals are wR2 = 0.0825 and R = 0.0347, S = 1.072 for all
5399 reflections and wR2 = 0.0790 and R = 0.0289 for
4757 reflections with F > 4σ(F).
Structures IIa and IIIb were solved by the direct interaction in IIa is confirmed by an increased CSbC
method and refined by the least-squares method in full- equatorial angle (138.57(9)°) (on the contact side) and
matrix anisotropic approximation for all reflections by the other two equatorial angles being respectively
with the use of the SHELXTL programs [6]. Hydrogen decreased to 109.13(9)° and 112.2(1)° relative to the
atoms were located geometrically.
perfect angle of 120°. The analogous angles in complex
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 5 2002

TETRA- AND TRIARYLANTIMONY FLUOROBENZOATES
335
Table 2. Coordinates (×104) and equivalent isotropic thermal parameters Uequiv (×103, Å2) of non-hydrogen atoms in struc-
tures IIa and IIIb
Atom
x
y
z
Uequiv
Atom
x
y
z
Uequiv
IIa
IIIb
Sb(1)
O(11)
O(21)
C(11)
C(21)
C(31)
C(41)
C(51)
C(61)
C(71)
F(31)
F(41)
F(51)
F(61)
F(71)
O(12)
O(22)
C(12)
C(22)
C(32)
C(42)
C(52)
C(62)
C(72)
F(32)
F(42)
F(52)
F(62)
F(72)
C(13)
C(23)
C(33)
C(43)
C(53)
C(63)
C(14)
C(24)
C(34)
C(44)
C(54)
C(64)
C(15)
C(25)
C(35)
C(45)
C(55)
C(65)
8483(1)
10275(2)
11217(2)
11276(2)
12582(2)
12650(3)
13871(4)
15059(3)
15025(3)
13810(3)
11516(2)
13905(3)
16247(3)
16193(2)
13826(2)
6646(2)
7602(2)
6628(3)
5238(2)
4032(3)
2789(3)
2683(3)
3844(3)
5092(3)
4060(2)
1658(2)
1475(2)
3750(2)
6174(2)
7420(2)
6023(3)
5328(3)
6009(3)
7386(3)
8102(3)
9394(2)
9072(3)
2541(1)
1914(2)
2417(2)
2020(2)
1576(2)
1820(3)
1419(4)
747(4)
3121(1)
3506(2)
1572(2)
2552(2)
2732(2)
3680(3)
3800(4)
2958(4)
2012(4)
1897(3)
4494(2)
4705(3) 121(1)
3063(3) 129(1)
1207(3) 112(1)
963(2)
2880(2)
906(2)
36(1)
42(1)
57(1)
42(1)
44(1)
56(1)
75(1)
79(1)
72(1)
55(1)
81(1)
Sb(1)
O(1)
O(2)
F(1)
F(2)
F(3)
F(4)
F(5)
–28(1)
–1851(2)
–2993(2)
9623(1)
9195(1)
9447(2)
1921(1)
2236(1)
1038(1)
2775(1)
3318(1)
40(1)
52(1)
67(1)
76(1)
89(1)
–3818(2) 10226(2)
–5734(2)
–6873(2)
–6156(3)
–4234(2)
–2839(3)
–3947(2)
–4363(3)
–5345(3)
–5929(3)
–5569(3)
–4586(3)
1589(2) 10041(2)
2101(3)
3078(3)
3599(3) 10661(2)
3090(3) 11119(2)
2103(3) 10818(2)
4653(3) 11002(3)
596(3)
1143(4) 10123(2)
1520(5) 10040(3)
1367(3)
850(3)
457(3)
1751(5)
–254(3)
484(3)
9786(2)
8300(2)
7304(2)
7751(2)
9236(2)
8994(2)
9490(2)
9271(3)
8536(3)
8029(2)
8262(2)
2874(2) 103(1)
1817(2) 115(1)
1261(2)
1716(2)
2013(2)
2535(2)
2825(2)
2593(2)
2057(3)
1774(2)
1594(2)
1084(2)
834(2)
1091(2)
1597(2)
1842(2)
808(2)
3136(2)
3586(2)
4386(2)
4760(2)
4311(2)
3504(2)
95(1)
49(1)
49(1)
53(1)
61(1)
67(1)
72(1)
62(1)
43(1)
47(1)
53(1)
50(1)
65(1)
65(1)
70(1)
43(1)
79(1)
96(2)
66(1)
65(1)
59(1)
483(3)
906(3)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(47)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(57)
2508(2)
1707(3)
365(3)
–181(3)
617(2)
81(1)
49(1)
55(1)
43(1)
41(1)
49(1)
56(1)
56(1)
52(1)
45(1)
73(1)
90(1)
84(1)
77(1)
69(1)
39(1)
70(1)
81(1)
59(1)
66(1)
57(1)
41(1)
52(1)
64(1)
62(1)
58(1)
51(1)
39(1)
54(1)
64(1)
61(1)
57(1)
48(1)
3103(2)
3309(2)
3373(2)
3808(2)
4496(3)
4914(3)
4645(3)
3966(3)
3567(2)
4787(2)
5568(3)
5035(2)
3679(2)
2885(2)
2299(2)
2894(4)
2790(4)
2117(3)
1521(4)
1619(3)
861(2)
9584(2)
9895(2)
1820(2)
1793(2)
2649(2)
2577(3)
1669(3)
815(3)
9464(2)
880(2)
3558(2)
3431(2)
1617(2)
–59(2)
9309(3)
8645(2)
8717(2)
9241(4)
8474(2)
7803(2)
7053(2)
6958(2)
7629(2)
8385(2)
6144(3)
34(2)
5643(2) 102(2)
4960(2)
5408(3)
6633(3)
7389(2)
6949(2)
5737(2)
2346(2)
3075(3)
2635(3)
1495(3)
774(3)
1181(2)
2610(2)
3477(3)
3219(3)
2128(3)
1268(3)
1494(2)
1292(2)
1603(2)
1198(2)
474(2)
170(2)
568(2)
23(3)
1613(2)
934(2)
730(2)
1196(2)
1877(2)
2086(2)
963(3)
43(1)
58(1)
66(1)
62(1)
64(1)
54(1)
96(1)
45(1)
59(1)
66(1)
58(1)
56(1)
50(1)
86(1)
434(4)
–338(3)
–1064(3)
–1033(3)
–342(5)
–959(3) 10771(2)
–859(3) 11170(2)
–1429(3) 11933(2)
–2073(3) 12326(2)
–2157(3) 11930(2)
–1610(3) 11152(2)
–2656(4) 13180(3)
–130(3)
9671(4) –1285(3)
10581(3) –1438(3)
10904(3)
10318(3)
8388(2)
8302(3)
8247(4)
8277(3)
8365(3)
8434(3)
–447(3)
716(3)
4402(2)
4932(3)
6145(3)
6822(3)
6297(3)
5077(3)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 5 2002

336
SHARUTIN et al.
Table 3. Bond lengths and angles in structures IIa and IIIb
IIa
IIIb
Bond
d, Å
Bond
d, Å
Bond
d, Å
Bond
d, Å
Sb(1)–C(13)
Sb(1)–C(14)
Sb(1)–O(11)
O(21)–C(11)
C(21)–C(31)
C(31)–F(31)
C(41)–F(41)
C(51)–F(51)
C(61)–F(61)
C(71)–F(71)
O(22)–C(12)
C(22)–C(72)
C(32)–F(32)
C(42)–F(42)
C(52)–F(52)
C(62)–F(62)
C(72)–F(72)
C(13)–C(63)
C(33)–C(43)
C(53)–C(63)
C(14)–C(64)
C(34)–C(44)
C(54)–C(64)
C(15)–C(25)
C(35)–C(45)
2.103(2)
2.108(2)
2.154(2)
1.206(3)
1.376(4)
1.338(4)
1.329(4)
1.336(4)
1.338(4)
1.333(4)
1.213(3)
1.386(3)
1.332(3)
1.348(3)
1.326(3)
1.332(3)
1.336(3)
1.376(3)
1.352(5)
1.384(4)
1.396(3)
1.369(5)
1.384(4)
1.389(4)
1.365(5)
Sb(1)–C(15)
Sb(1)–O(12)
O(11)–C(11)
C(11)–C(21)
C(21)–C(71)
C(31)–C(41)
C(41)–C(51)
C(51)–C(61)
C(61)–C(71)
O(12)–C(12)
C(12)–C(22)
C(22)–C(32)
C(32)–C(42)
C(42)–C(52)
C(52)–C(62)
C(62)–C(72)
C(13)–C(23)
C(23)–C(33)
C(43)–C(53)
C(14)–C(24)
C(24)–C(34)
C(44)–C(54)
C(15)–C(65)
C(25)–C(35)
C(45)–C(55)
2.105(2)
2.122(2)
1.296(3)
1.503(3)
1.388(4)
1.378(5)
1.375(6)
1.363(6)
1.362(5)
1.292(3)
1.510(3)
1.398(4)
1.370(4)
1.371(5)
1.372(4)
1.376(4)
1.376(4)
1.394(4)
1.357(4)
1.373(4)
1.394(4)
1.372(5)
1.387(3)
1.379(4)
1.374(5)
Sb(1)–C(51)
Sb(1)–C(41)
Sb(1)–O(1)
O(2)–C(11)
F(2)–C(14)
2.104(3) Sb(1)–C(31)
2.110(3) Sb(1)–C(21)
2.373(2) O(1)–C(11)
1.212(4) F(1)–C(13)
1.340(4) F(3)–C(15)
1.343(4) F(5)–C(17)
1.527(4) C(12)–C(13)
1.377(5) C(13)–C(14)
1.352(5) C(15)–C(16)
1.381(5) C(21)–C(26)
1.386(4) C(22)–C(23)
1.376(5) C(24)–C(25)
1.506(4) C(25)–C(26)
1.365(5) C(31)–C(36)
1.379(5) C(33)–C(34)
1.360(5) C(34)–C(37)
1.390(5) C(41)–C(46)
1.382(4) C(42)–C(43)
1.375(5) C(44)–C(45)
1.510(5) C(45)–C(46)
1.381(4) C(51)–C(56)
1.376(5) C(53)–C(54)
1.377(5) C(54)–C(57)
2.104(3)
2.160(3)
1.273(4)
1.338(4)
1.339(4)
1.342(4)
1.375(5)
1.380(5)
1.373(6)
1.384(5)
1.381(4)
1.379(5)
1.381(5)
1.372(4)
1.361(6)
1.515(5)
1.376(4)
1.376(5)
1.372(5)
1.382(5)
1.380(4)
1.372(5)
1.515(5)
F(4)–C(16)
C(11)–C(12)
C(12)–C(17)
C(14)–C(15)
C(16)–C(17)
C(21)–C(22)
C(23)–C(24)
C(24)–C(27)
C(31)–C(32)
C(32)–C(33)
C(34)–C(35)
C(35)–C(36)
C(41)–C(42)
C(43)–C(44)
C(44)–C(47)
C(51)–C(52)
C(52)–C(53)
C(54)–C(55)
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
C(13)Sb(1)C(14) 112.2(1) C(13)Sb(1)C(15) 109.13(9) C(51)Sb(1)C(41) 127.8(1) C(51)Sb(1)C(31) 113.1(1)
C(13)Sb(1)O(12) 87.53(8) C(15)Sb(1)C(14) 138.57(9) C(51)Sb(1)C(21) 94.4(1) C(31)Sb(1)C(41) 113.7(1)
C(14)Sb(1)O(12) 91.38(8) C(15)Sb(1)O(12) 92.73(8) C(41)Sb(1)C(21) 97.3(1) C(31)Sb(1)C(21) 101.9(1)
C(15)Sb(1)O(11) 89.77(8) C(13)Sb(1)O(11) 88.13(8) C(31)Sb(1)O(1)
O(12)Sb(1)O(11) 175.52(6) C(14)Sb(1)O(11) 89.20(8) C(21)Sb(1)O(1) 177.64(9) C(41)Sb(1)O(1)
O(21)C(11)O(11) 124.6(2) C(11)O(11)Sb(1) 111.3(2) O(2)C(11)O(1) 128.3(3) C(11)O(1)Sb(1)
O(11)C(11)C(21) 115.0(2) O(21)C(11)C(21) 120.4(2) O(1)C(11)C(12) 113.7(3) O(2)C(11)C(12)
80.22(9) C(51)Sb(1)O(1)
83.7(1)
82.80(9)
119.4(2)
118.0(3)
C(31)C(21)C(11) 123.6(2) C(31)C(21)C(71) 116.6(3) C(13)C(12)C(11) 122.1(3) C(13)C(12)C(17) 116.2(3)
F(31)C(31)C(21) 120.2(3) C(71)C(21)C(11) 119.8(2) F(1)C(13)C(12) 119.9(3) C(17)C(12)C(11) 121.7(3)
C(21)C(31)C(41) 121.9(3) F(31)C(31)C(41) 117.9(3) C(12)C(13)C(14) 123.0(3) F(1)C(13)C(14)
F(41)C(41)C(31) 120.4(4) F(41)C(41)C(51) 120.2(3) F(2)C(14)C(13) 120.8(4) F(2)C(14)C(15)
117.1(3)
120.1(3)
F(51)C(51)C(61) 120.2(4) C(51)C(41)C(31) 119.4(3) F(3)C(15)C(14) 120.5(4) C(15)C(14)C(13) 119.1(4)
C(61)C(51)C(41) 120.1(3) F(51)C(51)C(41) 119.7(4) C(14)C(15)C(16) 120.1(3) F(3)C(15)C(16)
F(61)C(61)C(51) 119.1(3) F(61)C(61)C(71) 121.2(4) F(4)C(16)C(17) 119.9(4) F(4)C(16)C(15)
119.4(4)
120.4(4)
F(71)C(71)C(61) 117.5(3) C(71)C(61)C(51) 119.7(3) F(5)C(17)C(12) 119.3(3) C(15)C(16)C(17) 119.7(3)
C(61)C(71)C(21) 122.3(3) F(71)C(71)C(21) 120.1(3) C(12)C(17)C(16) 121.8(3) F(5)C(17)C(16) 118.8(3)
O(22)C(12)O(12) 125.4(2) C(12)O(12)Sb(1) 119.8(2) C(26)C(21)Sb(1) 120.7(2) C(26)C(21)C(22) 117.0(3)
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TETRA- AND TRIARYLANTIMONY FLUOROBENZOATES
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Table 3. (Contd.)
IIa
IIIb
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
O(12)C(12)C(22) 113.6(2) O(22)C(12)C(22) 121.0(2) C(23)C(22)C(21) 121.2(3) C(22)C(21)Sb(1) 122.1(2)
C(72)C(22)C(12) 121.0(2) C(72)C(22)C(32) 115.8(2) C(23)C(24)C(25) 117.3(3) C(24)C(23)C(22) 121.6(3)
F(32)C(32)C(42) 117.7(2) C(32)C(22)C(12) 123.2(2) C(25)C(24)C(27) 121.2(3) C(23)C(24)C(27) 121.4(3)
C(42)C(32)C(22) 121.7(3) F(32)C(32)C(22) 120.6(2) C(25)C(26)C(21) 121.5(3) C(24)C(25)C(26) 121.4(3)
F(42)C(42)C(52) 119.9(3) F(42)C(42)C(32) 119.3(3) C(32)C(31)Sb(1) 119.7(2) C(32)C(31)C(36) 118.0(3)
F(52)C(52)C(42) 120.4(3) C(32)C(42)C(52) 120.8(3) C(31)C(32)C(33) 120.6(4) C(36)C(31)Sb(1) 122.3(2)
C(42)C(52)C(62) 119.1(2) F(52)C(52)C(62) 120.5(3) C(35)C(34)C(33) 117.4(3) C(34)C(33)C(32) 122.1(4)
F(62)C(62)C(72) 120.6(3) F(62)C(62)C(52) 119.5(3) C(33)C(34)C(37) 121.2(4) C(35)C(34)C(37) 121.4(4)
F(72)C(72)C(62) 116.4(2) C(52)C(62)C(72) 119.8(3) C(31)C(36)C(35) 120.6(3) C(34)C(35)C(36) 121.4(3)
C(62)C(72)C(22) 122.7(2) F(72)C(72)C(22) 120.9(2) C(46)C(41)Sb(1) 123.1(2) C(46)C(41)C(42) 119.1(3)
C(23)C(13)Sb(1) 119.9(2) C(23)C(13)C(63) 119.0(2) C(43)C(42)C(41) 120.5(3) C(42)C(41)Sb(1) 117.6(2)
C(13)C(23)C(33) 119.7(3) C(63)C(13)Sb(1) 121.0(2) C(45)C(44)C(43) 118.1(3) C(44)C(43)C(42) 120.9(3)
C(33)C(43)C(53) 119.5(3) C(43)C(33)C(23) 120.9(3) C(43)C(44)C(47) 120.2(4) C(45)C(44)C(47) 121.7(3)
C(13)C(63)C(53) 120.2(3) C(43)C(53)C(63) 120.8(3) C(41)C(46)C(45) 119.5(3) C(44)C(45)C(46) 121.9(3)
C(24)C(14)Sb(1) 116.0(2) C(24)C(14)C(64) 120.7(2) C(52)C(51)Sb(1) 118.4(2) C(52)C(51)C(56) 119.5(3)
C(14)C(24)C(34) 119.2(3) C(64)C(14)Sb(1) 123.2(2) C(53)C(52)C(51) 119.7(3) C(56)C(51)Sb(1) 122.0(2)
C(34)C(44)C(54) 119.9(3) C(44)C(34)C(24) 120.6(3) C(53)C(54)C(55) 118.4(3) C(54)C(53)C(52) 121.7(3)
C(54)C(64)C(14) 118.6(3) C(44)C(54)C(64) 120.9(3) C(55)C(54)C(57) 121.5(3) C(53)C(54)C(57) 120.2(3)
C(65)C(15)Sb(1) 124.5(2) C(65)C(15)C(25) 120.5(2) C(51)C(56)C(55) 119.9(3) C(54)C(55)C(56) 120.9(3)
C(35)C(25)C(15) 119.1(3) C(25)C(15)Sb(1) 115.1(2)
C(35)C(45)C(55) 120.1(3) C(45)C(35)C(25) 120.8(3)
C(55)C(65)C(15) 118.8(3) C(45)C(55)C(65) 120.7(3)
IIe are 150.0°, 104.8°, and 105.2°, which is consistent 5.1°), while the third phenyl ligand is rotated through
with the shorter Sb···O(=C) distances.
73.2°.
The benzoato fragments containing o-F atoms in the
aryl ring of the acyl substituent are not planar; the tor-
sion angles between the carboxy and aryl planes are
40.3(1)° and 32.2(1)° for the O(11)–C(71) and O(12)–
C(72) fragments, respectively. The corresponding tor-
sion angles in complexes IIa and IIe are 9.4(1)° and
13.0°, respectively; i.e., their carboxy and aryl groups
lie in nearly the same plane. Conformational differ-
ences in the equatorial phenyl substituents are notewor-
thy. In IIa, only one of them (C(14)–C(64)) is in the
equatorial plane (the corresponding torsion angle is
7.8(1)°), while the other values are 30.9(1)° and
72.7(1)°. In IIe, the planes of two phenyl substituents
The trigonal-bipyramidal configuration is signifi-
cantly distorted in tetra-p-tolylantimony pentafluo-
robenzoate IIIb (Fig. 2). The axial angle is 177.64(9)°,
while the equatorial angles range from 113.1(1)° to
127.8(1)°, their sum being equal to 354.7(1)°. The OSbCeq
angles are less than 90° (80.2(1)° to 83.7(1)°), while
the CaxSbCeq angles are 94.4(1)° to 101.9(1)°. The Sb–
Ceq bond lengths range from 2.104(3) to 2.110(3) Å; the
Sb–Cax bond is slightly longer (2.160(3) Å). The Sb–
Ceq and Sb–Cax bond lengths in tetraphenylantimony
benzoate IIIe are 2.125–2.129 and 2.172 Å, respec-
tively [3]; the angles with a vertex at the Sb atom are
are virtually coplanar to the equatorial plane (1.9° and close to those in IIIb.
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338
SHARUTIN et al.
F(52)
C(52)
C(42)
F(42)
F(62)
F(72)
C(62)
C(72)
C(32)
F(32)
C(22)
C(12)
O(22)
C(55)
O(212)
O(12)
C(45)
C(23)
C(33)
C(35)
C(65)
C(15)
Sb(1)
C(13)
C(14)
C(25)
O(11)
C(64)
C(43)
C(54)
C(44)
C(24)
C(63)
C(53)
C(34)
O(21)
C(11)
F(31)
F(71)
F(61)
C(21)
C(31)
C(71)
C(61)
C(41)
F(41)
C(51)
F(51)
Fig. 1. General view of the molecule of triphenylantimony bis(pentafluorobenzoate) (IIa).
The Sb–O bond lengths in tetraarylantimony acy- ment of substituents in the aroxy group and determines
lates IIIb and IIIe (2.373(2) and 2.243 Å, respectively)
significantly exceed the sum of the covalent radii of
antimony and oxygen (2.07 Å [9]), indicating that this
bond is polar, especially in compound IIIb.
the electron density transfer from antimony to oxygen
and, therefore, the Sb–O bond length. Apparently, the
Sb–O distance in tetraarylantimony acylates also
depends on the apparent charge on the oxygen atom
bound to antimony. The electron density on the
hydroxy O atom is determined (1) by the induction
effect of the CO group, (2) by the conjugation of the π
In aroxytetraphenylantimony complexes, a lone
electron pair on the oxygen atom can interact with the
π electron system of the arene ring [12]. The intensity
of this interaction depends on the nature and arrange- electrons of the CO group with the lone electron pairs
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TETRA- AND TRIARYLANTIMONY FLUOROBENZOATES
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F(3)
F(4)
C(15)
C(16)
F(2)
C(17)
C(14)
F(5)
C(13)
C(12)
F(1)
C(11)
O(2)
C(45)
O(1)
C(44)
C(42)
C(47)
C(43)
C(46)
C(56)
C(55)
C(54)
C(41)
C(35)
C(36)
Sb(1)
C(51)
C(57)
C(31)
C(52)
C(53)
C(34)
C(37)
C(21)
C(32)
C(22)
C(33)
C(26)
C(23)
C(24)
C(27)
C(25)
Fig. 2. General view of the molecule of tetra-p-tolylantimony pentafluorobenzoate (IIIb).
of the hydroxy O atom, and (3) by the nature and struc- der Waals radii (3.309(3) Å versus 3.7 Å), but it is still
longer than the Sb···O(=C) distances in compound IIa.
ture of the radical R. The first two factors decrease the
electron density on the hydroxy O atom, while the rad-
ical R can both increase and lower the charges on the
carboxy O atoms, depending on the sign and magnitude
of its effects. In the fluorinated phenyl radical, which is
a significantly stronger electron acceptor, the charge on
the hydroxy O atom decreases. This results in an elec-
tron density transfer from the Sb atom and makes the
Sb–O bond in IIIb longer than that in IIIe.
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