Tri- and tetraphenylantimony propiolates: Syntheses and structures

Article abstract of DOI:10.1134/S1070328414020109

The reaction of triphenylantimony with propiolic acid in the presence of hydrogen peroxide (molar ratios 1: 2: 1 and 1: 1: 1) in diethyl ether affords triphenylantimony dipropiolate Ph₃Sb[OC(O)C≡CH]₂ (I) and μ₂-oxobis[(propiolato)triphenylantimony] [Ph ₃SbOC(O)C≡CH]₂O (II). Tetraphenylantimony propiolate Ph₄SbOC(O)C≡CH (III) is synthesized from pentaphenylantimony and propiolic or acetylenedicarboxylic acid in toluene. According to the X-ray diffraction data, the crystals of compounds I and III include two types of crystallographically independent molecules (a and b). The antimony atoms in molecules Ia, Ib, II, IIIa, and IIIb have the trigonal-bipyramidal coordination mode with different degrees of distortion. The OSbO and OSbC axial angles are 176.8(2)° (Ia, Ib), 170.17(15), 178.78(14) ° (II), and 173.2(5) °, 174.4(5) ° (IIIa, IIIb). The CSbC equatorial angles lie in the ranges 108.2(3) ° -143.1(3) ° (I), 109.0(2) ° -131.0(2) ° (II), and 113.1(4) ° -125.4(4) ° (III). The SbOSb angle in II is 141.55(19) °. The Sb-C bond lengths are 2.103(8)-2.141(5) (I), 2.105(5)-2.119(5) (II), and 2.076(12)-2.166(13) A (III). The Sb-O distances increase in a series of I, II, and III: 2.139(6)-2.156(7) (Ia, Ib); 2.206(4), 2.218(3) (II); and 2.338(10), 2.340(10) A (III).

Full text of DOI:10.1134/S1070328414020109

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2014, Vol. 40, No. 2, pp. 109–114. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © V.V. Sharutin, O.K. Sharutina, V.S. Senchurin, 2014, published in Koordinatsionnaya Khimiya, 2014, Vol. 40, No. 2, pp. 108–112.
Triꢀ and Tetraphenylantimony Propiolates:
Syntheses and Structures
V. V. Sharutin*, O. K. Sharutina, and V. S. Senchurin
National Research Southern Ural State University, Chelyabinsk, Russia
*eꢀmail: vvsharutin@rambler.ru
Received June 26, 2013
Abstract—The reaction of triphenylantimony with propiolic acid in the presence of hydrogen peroxide
(molar ratios 1 : 2 : 1 and 1 : 1 : 1) in diethyl ether affords triphenylantimony dipropiolate
Ph3Sb[OC(O)C
raphenylantimony propiolate Ph4SbOC(O)C
piolic or acetylenedicarboxylic acid in toluene. According to the Xꢀray diffraction data, the crystals of comꢀ
pounds and III include two types of crystallographically independent molecules ( and ). The antimony
atoms in molecules Ia Ib II IIIa, and IIIb have the trigonal–bipyramidal coordination mode with different
degrees of distortion. The OSbO and OSbC axial angles are 176.8(2)° (Ia Ib), 170.17(15) , 178.78(14) II),
and 173.2(5) , 174.4(5) IIIa IIIb). The CSbC equatorial angles lie in the ranges 108.2(3) –143.1(3) I)
109.0(2) –131.0(2) II), and 113.1(4) –125.4(4) III). The SbOSb angle in II is 141.55(19) . The Sb–C
bond lengths are 2.103(8)–2.141(5) ( ), 2.105(5)–2.119(5) (II), and 2.076(12)–2.166(13) Å (III). The Sb
II, and III: 2.139(6)–2.156(7) (Ia Ib); 2.206(4), 2.218(3) (II); and
≡CH]2
(
I
) and μ2ꢀoxobis[(propiolato)triphenylantimony] [Ph3SbOC(O)C
≡CH]2O (II). Tetꢀ
≡
CH III) is synthesized from pentaphenylantimony and proꢀ
(
I
a
b
,
, ,
,
°
° (
° ( ,
°
°
(
,
°
°
°
(
°
°
(
°
I
⎯O
distances increase in a series of
2.338(10), 2.340(10) Å (III).
I,
,
DOI: 10.1134/S1070328414020109
INTRODUCTION
IR, ν
, cm–1: 3274, 3067, 2360, 2189, 2106, 1640,
1576, 1542, 1480, 1436, 1292, 1185, 1164, 1070, 1021,
996, 903, 843, 773, 735, 685, 667, 631, 592, 461.
The antimony(V) phenyl derivatives containing
carboxylate ligands of the type Ph4SbOC(O)R and
Ph3Sb[OC(O)R]2 are studied fairly well [1, 2], whereas
compounds [Ph3SbOC(O)R]2О are investigated to a
lower extent [3–6]. It is known that carboxylate
ligands, as a rule, are anisobidentate. The asymmetry
of the coordination mode of the same ligand in comꢀ
pounds of different types can strongly differ. In tetꢀ
For C24H17O4Sb
anal. calcd., %:
Found, %:
C, 58.69;
C, 58.53;
H, 3.46.
H, 3.54.
Synthesis of II. A 30% aqueous solution of hydroꢀ
gen peroxide (0.096 g) was added to a mixture of triphꢀ
enylantimony (0.30 g, 0.85 mmol) and propiolic acid
(0.06 g, 0.85 mmol) in diethyl ether (15 mL), and the
raphenylantimony acetate the Sb–O and Sb⋅⋅⋅
O disꢀ
tances are 2.234 and 2.594 Å [7], whereas they are
2.130 and 2.780 Å in triphenylantimony diacetate [8].
The purpose of this work is the synthesis of tripheꢀ
mixture was kept for 24 h at 20°С. The formed finely
nylantimony dipropiolate Ph3Sb[OC(O)C
), μ2 μ2ꢀoxobis[(propiolato)triphenylantimony]
[Ph3SbOC(O)C СН]2O (II), and tetraphenylantiꢀ
mony propiolate Ph4SbOC(O)C СН (III and the
≡СН]2
crystalline powder was recrystallized from toluene.
The yield of colorless crystals of compound II was
0.29 g (80%); m.p. = 166°C (with decomposition).
(
I
,
≡
≡
)
IR, ν
, cm–1: 3274, 3053, 2106, 1640, 1576, 1480,
elucidation of regularities of the coordination mode of
the carboxylate ligands, depending on the type of the
compound.
1435, 1386, 1292, 1185, 1071, 1021, 997, 896, 773,
734, 716, 688, 667, 631, 615, 458.
For C42H32O5Sb2
EXPERIMENTAL
anal. calcd., %:
Found, %:
C, 58.64;
C, 58.48;
H, 3.72.
H, 3.80.
Synthesis of I. A 30% aqueous solution of hydrogen
peroxide (0.096 g) was added to a mixture of triphenylꢀ
antimony (0.30 g, 0.85 mmol) and propiolic acid
Synthesis of III. (A) A mixture of pentaphenylantiꢀ
(0.12 g, 1.70 mmol) in diethyl ether (15 mL), and the mony (0.50 g, 0.99 mmol) and propiolic acid (0.07 g,
mixture was kept for 24 h at 20 . The yield of colorꢀ 0.99 mmol) in toluene (10 mL) was heated for 1 h in a
less crystals of compound
146°C (with decomposition).
°С
I
was 0.38 g (91%); m.p. = boiling water bath, then the bath and the mixture were
cooled down, and the solvent was removed. The yield
109

110
SHARUTIN et al.
Table 1. Crystallographic data and the experimental and refinement parameters for structures I–III
Value
Parameter
I
II
III
M
491.13
296(2)
860.18
296(2)
998.38
273.15
T
, K
Crystal system
Triclinic
Monoclinic
Triclinic
P
21/c
Space group
P
1
P1
a
b
, Å
, Å
8.085(6)
8.155(3)
17.234(9)
100.75(4)
99.92(5)
102.84(4)
1061.0(10)
2
20.062(6)
9.996(4)
19.739(5)
90.00
110.36(2)
90.00
10.2129(12)
10.2899(12)
12.7441(16)
78.951(4)
66.758(4)
68.055(3)
1139.9(2)
2
c
α
, Å
, deg
, deg
, deg
β
γ
V
Z
, Å3
3711(2)
4
ρcalcd, g/cm3
, mm–1
(000)
Crystal size, mm
Range for data collection, deg
1.537
1.326
488.0
1.539
1.499
1704.0
1.454
1.230
500.0
× 0.16 × 0.09
μ
F
0.19
×
0.14
×
0.03
0.32
×
0.22
×
0.14
0.48
θ
5.26–61.12
4.34–61.86
5.66–49.48
Ranges of reflection indices
–11
–9
–24
≤
≤
≤
h
k
l
≤
≤
≤
8,
11,
24
–16
–14
–28
≤
≤
≤
h
k
l
≤
≤
≤
29,
13,
28
–11
–11
–14 ≤ l
≤
≤
h
k
≤
≤
≤
11,
12,
14
Measured reflections
Independent reflections
Rint
11748
7629
0.0436
523
41045
11598
0.0545
442
61919
7525
0.0513
541
Refinement variables
Goodnessꢀofꢀfit
1.082
1.092
1.073
R
R
factors for F 2 > 2
σ(
F 2
)
R
R
1 = 0.0517, wR2 = 0.0867
1 = 0.0927, wR2 = 0.0991
1.26/–1.26
R
R
1 = 0.0589, wR2 = 0.0930
1 = 0.1158, wR2 = 0.1142
1.66/–1.74
R
R
1 = 0.0237, wR2 = 0.0548
1 = 0.0285, wR2 = 0.0568
0.58/–0.39
factors for all reflections
Residual electron density (min/max),
/Å3
e
of colorless crystals of compound III was 0.41 g (83%);
m.p. = 174°C (with decomposition).
IR spectra were recorded on a Bruker Tensor 27
FTꢀIR spectrometer (pellets with KBr).
(B) A mixture of pentaphenylantimony (0.250 g,
0.49 mmol) and acetylenedicarboxylic acid (0.056 g,
0.49 mmol) in toluene (5 mL) was heated for 1 h in a
boiling water bath. Then the mixture was cooled
down, and the solvent was removed. The yield of colꢀ
orless crystals of compound III was 0.214 g (87%);
m.p. =174°C (with decomposition).
Xꢀray diffraction analyses for crystals I–III were
carried out on a D8 QUEST diffractometer (Bruker,
MoKα radiation,
λ = 0.71073 Å, graphite monochroꢀ
mator). Data were collected and edited, unit cell
parameters were refined, and an absorption correction
was applied using the SMART and SAINTꢀPlus proꢀ
grams [9]. All calculations on the determination and
IR, ν
, cm–1: 3277, 3053, 3010, 2990, 2917, 2591, 2361,
refinement of structure
I were performed using the
2178, 2091, 1967, 1885, 1819, 1621, 1575, 1562, 1477,
1433, 1377, 1333, 1301, 1187, 1158, 1070, 1057, 1020,
997, 883, 782, 737, 693, 658, 643, 601, 586, 462, 447.
SHELXL/PC programs [10]. The structures were
determined by a direct method and refined by least
squares in the anisotropic approximation for nonꢀ
hydrogen atoms. The main crystallographic data and
the refinement results for I–III are presented in
Table 1. Selected bond lengths and bond angles are
given in Table 2.
For C27H21O2Sb
anal. calcd., %:
Found, %:
C, 64.96;
C, 64.81;
H, 4.21.
H, 4.29.
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TRIꢀ AND TETRAPHENYLANTIMONY PROPIOLATES
111
Table 2. Selected bond lengths and bond angles in strucꢀ
tures III
The full tables of atomic coordinates, bond lengths,
and bond angles for structures I–III were deposited
with the Cambridge Crystallographic Data Centre
(nos. 940655–940657; deposit@ccdc.cam.ac.uk;
http://www.ccdc.cam.ac.uk).
I–
Bond
d
, Å
Angle
ω, deg
I
Sb(1)–O(3)
Sb(1)–C(21)
Sb(1)–O(1)
Sb(1)–C(11)
Sb(1)–C(1)
Sb(2)–O(5)
Sb(2)–O(7)
Sb(2)–C(31)
Sb(2)–C(41)
Sb(2)–C(51)
O(3)–C(17)
O(2)–C(27)
O(5)–C(57)
O(1)–C(27)
O(7)–C(47)
O(8)–C(47)
C(17)–O(4)
O(6)–C(57)
2.156(7) C(21)Sb(1)O(3)
2.109(9) C(21)Sb(1)O(1)
2.152(7) C(21)Sb(1)C(1) 109.4(3)
2.103(8) O(1)Sb(1)O(3)
2.138(5) C(11)Sb(1)O(3)
2.139(6) C(11)Sb(1)C(21) 142.4(4)
2.141(6) C(11)Sb(1)O(1) 89.5(3)
2.124(9) C(11)Sb(1)C(1) 108.2(3)
2.118(9) C(1)Sb(1)O(3)
2.141(5) C(1)Sb(1)O(1)
1.308(9) O(5)Sb(2)O(7)
1.233(10) O(5)Sb(2)C(51)
1.321(9) O(7)Sb(2)C(51)
1.320(10) C(31)Sb(2)O(5)
1.306(9) C(31)Sb(2)O(7)
89.7(3)
91.1(3)
RESULTS AND DISCUSSION
Triphenylantimony dipropiolate (I) and μ2ꢀoxoꢀ
176.8(2)
91.8(3)
bis[(propiolato)triphenylantimony] (II) were syntheꢀ
sized from triphenylantimony and propiolic acid in
the presence of hydrogen peroxide at different molar
ratios (1 : 2 : 1 and 1 : 1 : 1, respectively)
Ph3Sb + 2HOC(O)C≡CH + H2O2 →
88.4(2)
88.4(2)
176.8(2)
89.1(2)
87.7(2)
90.7(3)
89.9(3)
→ Ph3Sb[OC(O)C≡CH]2 + H2O,
2Ph3Sb + HOC(O)C≡CH + 2H2O2 →
→ [Ph3SbOC(O)C≡CH]2O + H2O.
Tetraphenylantimony propiolate (III) was syntheꢀ
sized by the dephenylation of pentaphenylantimony
with propiolic acid on heating in a toluene solution
(1 h, 100°C)
1.230(10) C(31)Sb(2)C(51) 108.7(3)
Ph5Sb + HOC(O)C≡CH →
1.232(9) C(41)Sb(2)O(5)
1.227(9) C(41)Sb(2)O(7)
II
2.206(4) O(1)Sb(1)O(2)
1.975(3) O(1)Sb(1)C(11)
2.106(5) O(1)Sb(1)C(21)
2.105(5) C(1)Sb(1)O(2)
2.112(5) C(1)Sb(1)C(21) 122.8(2)
1.982(3) C(11)Sb(1)C(1) 116.5(2)
2.120(5) C(11)Sb(1)C(21) 119.8(2)
89.7(3)
91.8(3)
→ Ph4SbOC(O)C≡CH + PhH.
Product III is also formed by the reaction of penꢀ
taphenylantimony with acetylenedicarboxylic acid,
which evidently undergoes decarboxylation under the
reaction conditions
Sb(1)–O(2)
Sb(1)–O(1)
Sb(1)–C(1)
Sb(1)–C(11)
Sb(1)–C(21)
Sb(2)–O(1)
170.17(15)
97.40(18)
91.06(17)
86.69(19)
Ph Sb + HOC(O)C≡CC O OH → III + CO + PhH.
( )
5
2
According to the Xꢀray diffraction data, the crystals
of compounds and III include two types of crystalloꢀ
graphically independent molecules ( and ). The
antimony atoms in molecules Ia Ib II
I
a
,
b
,
,
IIIa, and IIIb Sb(2)–C(41)
have the trigonal–bipyramidal coordination mode
with different degrees of distortion (figure). The axial
positions of molecules Ia and Ib contain the oxygen
atoms of the carboxylate ligands, those of molecules II
contain the oxygen atoms (bridging and carboxylate),
and the axial positions of molecules IIIa and IIIb conꢀ
tain the carbon atom of the phenyl group and the carꢀ
boxylate oxygen atom. The OSbO axial angles in comꢀ
pounds Ia and Ib coincide (176.8(2)°) and substanꢀ
tially differ in two fragments of molecule II
Sb(2)–C(31)
Sb(2)–C(51)
Sb(2)–O(4)
O(2)–C61
C(61)–O(3)
O(4)–C(64)
C(64)–O(5)
2.119(5) C(21)Sb(1)O(2)
2.109(5) O(1)Sb(2)C(31)
2.218(3) O(1)Sb(2)O(4)
1.286(6) C(31)Sb(2)C(41) 118.7(2)
1.217(7) C(51)Sb(2)C(41) 131.0(2)
1.303(6) C(51)Sb(2)C(31) 109.03(19)
82.13(18)
96.44(17)
178.78(14)
1.214(7) C(51)Sb(2)O(4)
87.99(16)
III
Sb(1)–C(1)
Sb(1)–C(21)
Sb(1)–C(31)
Sb(1)–C(11)
Sb(1)–O(1)
Sb(2)–O(3)
2. 082(11) C(1)Sb(1)C(21) 113.1(4)
2.136(10) C(1)Sb(1)C(31) 125.4(4)
2.076(12) C(31)Sb(1)C(11) 97.9(5)
2.166(13) C(31)Sb(1)C(21) 117.1(5)
2.338(10) C(31)Sb(1)O(1)
2.340(10) C(11)Sb(1)O(1) 174.4(5)
2.140(11) C(41)Sb(2)O(3) 80.5(4)
(O(2)Sb(1)O(1)
170.17(15)°,
O(4)Sb(2)O(1)
178.78(14)°). The CaxSbO angles in molecules IIIa
and IIIb are similar (174.4(5)° and 173.2(5)°)
(Table 2). The substantial distortion of the
O(2)Sb(1)O(1) angle in structure II can be explained
by the deviation of the Sb(1)–O(2) and Sb(1)–O(1)
81.8(4)
axial bonds from the C(11)–C(16) phenyl Sb(2)–C(41)
group, whose plane almost coincides with the equatoꢀ
rial plane C(1)C(11)C(21) (the angle between
them is only 8.92°). The O(2)Sb(1)C(11) and
O(1)Sb(1)C(11) angles are 92.16(18)° and 97.40(18)°.
In molecules Ia and Ib, the antimony atoms shift
from the equatorial plane by 0.006 and 0.003 Å. In
structure II, the Sb(1) and Sb(2) atoms are shifted to
the bridging oxygen atom by 0.115 and 0.137 Å,
Sb(2)–C(71)
Sb(2)–C(61)
Sb(2)–C(51)
O(2)–C(37)
O(3)–C(77)
O(4)–C(77)
O(1)–C(37)
2.151(10) C(41)Sb(2)C(71) 124.0(4)
2.163(12) C(41)Sb(2)C(51) 116.4(4)
2.056(11) C(61)Sb(2)O(3) 173.2(5)
1.198(17) C(61)Sb(2)C(41) 95.4(4)
1.312(16) C(61)Sb(2)C(71) 98.9(5)
1.253(17) C(61)Sb(2)C(51) 97.0(5)
1.278(14) C(51)Sb(2)C(71) 115.0(4)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
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112
SHARUTIN et al.
respectively. In structures IIIa and IIIb, the antimony 2.116(5) Å (II); 2.076(12)–2.136(10), 2.099(11) Å
atoms deviate to the axial carbon atom by 0.255 and IIIa); and 2.056(11)–2.151(10), 2.116(10) Å (IIIb).
0.262 Å, respectively. The sums of the angles in the The Sb–Cax axial bonds (2.166(13) in IIIa and
(
equatorial plane are 360.0° (Ia), 359.1° (Ib), 358.7°
2.163(12) Å in IIIb) are longer than the equatorial
bonds.
(II), 355.6°(IIIa), and 355.4° (IIIb).
The ranges of changing the Sb–Ceq bond lengths
In a series of compounds I, II, and III, the bond
and their average values are 2.103(8)–2.138(5), between the antimony atom and the oxygen atom of
2.117(8) Å (Ia); 2.118(9)–2.141(5), 2.128(8) Å (Ib); the Sn–O carboxylate ligand elongates: 2.156(7),
2.105(5)–2.112(5), 2.108(5) and 2.109(5)–2.120(5), 2.152(7) Å (Ia); 2.139(6), 2.141(6) Å (Ib); 2.206(4),
C(54)
C(55)
C(4)
C(53)
C(52)
C(3)
C(2)
C(56)
C(5)
C(6)
C(51)
C(43)
C(1)
O(3)
C(23)
C(42)
C(22)
C(16)
O(7)
Sb(2)
C(57)
C(15)
C(41)
C(58)
C(32)
C(48)
C(19)
O(5)
C(18)
C(17)
C(44)
C(45)
Sb(1)
C(11)
C(21)
O(4)
C(59)
C(14)
O(1)
C(47)
C(46)
C(24)
C(25)
C(31)
C(49)
C(33)
C(12)
C(26)
C(27)
C(13)
C(34)
C(36) O(8)
O(6)
C(28)
O(2)
C(29)
C(35)
Iа
Ib
C(4)
C(5)
C(6)
C(33)
C(32)
C(3)
C(2)
C(34)
C(55)
C(35)
C(54)
C(1)
C(31)
C(56)
O(3)
C(16)
Sb(2)
O(1)
C(61)
C(53)
C(52)
Sb(1 )
C(21)
C(62)
C(63)
O(2)
O(4)
C(15)
C(14)
C(26)
C(23)
C(65)
C(41)
C(64)
O(5)
C(25)
C(13)
C(66)
C(46)
C(45)
C(24)
C(42)
C(43)
C(44)
II
General view of molecules I–III
.
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TRIꢀ AND TETRAPHENYLANTIMONY PROPIOLATES
113
С(75)
С(14)
С(15)
С(78)
С(79)
С(13)
С(12)
С(74)
С(73)
С(76)
С(71)
С(77)
O(3)
O(4)
С(16)
С(26)
С(25)
С(32)
С(11)
С(24)
С(21)
С(33)
С(56)
С(55)
С(72)
С(34)
С(35)
С(46)
Sb(2)
Sb(1)
С(31)
С(36)
С(45)
С(51)
С(2)
С(61)
С(54)
С(52)
С(53)
С(22)
O(2)
С(44)
O(1)
С(1)
С(66)
С(3)
С(4)
С(62)
С(37)
С(65)
С(6)
С(63)
С(38)
С(64)
С(5)
С(39)
IIIa
IIIb
Figure. (Contd.).
2.218(3) Å (II); and 2.338(10) (IIIa), 2.340(10) Å 1.982(3) Å and the Sb(1)O(1)Sb(2) angle is
(
IIIb).
141.55(19)°. Analogous parameters have similar values
in four structurally characterized complexes of
μ2ꢀoxobis[(carboxylato)triphenylantimony] [3–6].
The carboxylate ligands exhibit the anisobidentate
properties. The distances between the antimony atom
and the carbonyl oxygen atoms (Sb⋅⋅⋅O=C) in comꢀ
pounds Ia and Ib are 2.962(7), 2.976(7) Å and
2.977(6), 2.936(6) Å, respectively. In molecules IIIa
and IIIb, the interactions of the central atom with the
carbonyl oxygen atom are considerably weaker (the
Sb⋅⋅⋅O=C distances are 3.373(18) and 3.384(18) Å). In
molecule II, the intramolecular contacts differ
(3.613(4) and 3.076(3) Å), and the Sb(1)⋅⋅⋅O(3) value is
close to the sum of van der Waals radii of the Sb and
O atoms (3.7 Å [11]), which is evidently due to the
geometric factor: the coordination mode of the ligand
could be usual for a larger O(2)Sb(1)O(1) axial angle.
The asymmetry of the coordination mode of the carꢀ
boxylate ligands can be estimated by the ratio
A crystal of compound
ular hydrogen bonds involving the acetylenic hydroꢀ
gen atom С–Н⋅⋅⋅О–С (Н⋅⋅⋅О 2.69–2.71 . The
threeꢀdimensional structure of crystal II is formed by
the contacts meta Ph⋅⋅⋅О=С 2.60–2.68 and
meta Ph⋅⋅⋅О–С 2.61 Å; in addition, there is the hydroꢀ
I includes weak intermolecꢀ
Å)
Н
Å
Н
gen bond С(63)–Н(63)⋅⋅⋅О(3) 2.36 Å between the
acetylenic hydrogen atom and the carbonyl oxygen
atom. A crystal of compound III includes the
С⎯Н⋅⋅⋅О=С contacts between the hydrogen atoms of
the phenyl rings and the oxygen atoms of the carboxyꢀ
late ligands (2.45–2.69 Å).
Thus,
Ph3Sb[OC(O)C
Ph4SbOC(O)C
in
the
series
of
СН]2, [Ph3SbOC(O)C
compounds
СН]2O, and
≡
≡
≡
СН the distortion of the trigonal–
d
(Sb···O=C)/d(Sb–О), which is equal to 1.374, 1.379
bipyramidal coordination mode of the central atom
increases, which appears as its increasing deviation
from the equatorial plane and the elongation of the
Sb–O axial bonds, and the asymmetry of the coordiꢀ
nation mode of the carboxylate ligand also increases.
(
(
Ia); 1.371, 1.392 (Ib); 1.387, 1.638 (II); and 1.443
IIIa), 1.446 (IIIb).
Note that the Sb···O=C intramolecular interactions
result in the distortion of the CSbC equatorial angles
compared to the theoretical value. The angle at the
side of the contacts increases due to a decrease in two
other angles: 142.4(4)
131.0(2) II); and 125.4(4)
The sequence of increasing the CSbC angles in comꢀ
pounds III II, and is reciprocal to the sequence of
the elongation of the Sb··· distance.
In the central fragment of compound II, the
Sb(1,2)–O(1) bond lengths are 1.975(3) and
°
(
Iа), 143.1(3)° (Ib); 122.9(2)
°,
REFERENCES
°
(
° (
IIIа), 124.0(4)° (IIIb).
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,
I
O
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−
Translated by E. Yablonskaya
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
No. 2
2014