Synthesis and structure of tetraphenylantimony oximates Ph 4SbON=CRR′ (CRR′ = C6H9-C 6H9-2 and R = Ph, R′ = C(O)Ph)

Article abstract of DOI:10.1023/B:RUCO.0000037435.99654.0a

The reaction of pentaphenylantimony and the oxime HON=CRR′ taken in 1:1 molar ratio in toluene gave tetraphenylantimony oximates Ph ₄SbON=CRR′ (CRR′ = C₆H₉-C ₆H₉-2 (I) and R = Ph, R′ = C(O)Ph (II)). According to X-ray diffraction data, the Sb atoms in I and II have a distorted trigonal-bipyramidal coordination with oximate ligands in the axial positions. The C_axSbO angles are 177.6(1)° in I and 176.58(6)° in II. The Sb-C bond lengths lie in the ranges of 2.120(4)-2.203(4) for I and 2.122(2)-2.181(2) for II. The Sb-O bond lengths are 2.120(2) (I) and 2.166(1) (II). The lengths of the intramolecular Sb···N contacts are 2.806(3) and 2.918(2) in I and II, respectively.

Full text of DOI:10.1023/B:RUCO.0000037435.99654.0a

Russian Journal of Coordination Chemistry, Vol. 30, No. 8, 2004, pp. 559–565. Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 8, 2004, pp. 596–602.
Original Russian Text Copyright © 2004 by Sharutin, Molokova, Sharutina, Akimova, Gerasimenko, Pushilin.
Synthesis and Structure of Tetraphenylantimony Oximates
Ph4SbON=CRR' (CRR' = C6H9–C6H9-2 and R = Ph, R' = C(O)Ph)
V. V. Sharutin*, O. V. Molokova*, O. K. Sharutina*, T. I. Akimova**, A. V. Gerasimenko***,
and M. A. Pushilin***
*Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
** Far East State University, ul. Sukhanova 8, Vladivostok, 690600 Russia
*** Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
Received June 2, 2003
Abstract—The reaction of pentaphenylantimony and the oxime HON=CRR' taken in 1 : 1 molar ratio in tolu-
ene gave tetraphenylantimony oximates Ph4SbON=CRR' (CRR' = C6H9–C6H9-2 (I) and R = Ph, R' = C(O)Ph
(II)). According to X-ray diffraction data, the Sb atoms in I and II have a distorted trigonal-bipyramidal coor-
dination with oximate ligands in the axial positions. The CaxSbO angles are 177.6(1)° in I and 176.58(6)° in II.
The Sb–C bond lengths lie in the ranges of 2.120(4)–2.203(4) Å for I and 2.122(2)–2.181(2) Å for II. The Sb–
O bond lengths are 2.120(2) Å (I) and 2.166(1) Å (II). The lengths of the intramolecular Sb···N contacts are
2.806(3) and 2.918(2) Å in I and II, respectively.
The coordination number of the central atom in tet- dal surrounding formed by the O atoms of the oximate
raphenylantimony oximates Ph4SbON=CRR' is known
to increase to six due to additional coordination of the
oximate nitrogen atom to antimony atom [1–4]. Evi-
dently, the probability of Sb···N coordination in these
compounds can be decreased by introducing an addi-
tional coordination site into the oximate ligand. A
ligands (Figs. 1, 2). The axial CSbO angles are 177.6(1)°
in I and 176.58(6)° in II (Table 1). The OSbCeq bond
C(35)
decrease in the Sb
N donor–acceptor interaction
C(25)
C(24)
can also be expected in tetraphenylantimony oximates
having bulky substituents near nitrogen atom.
C(34)
C(33)
C(36)
C(26)
C(23)
C(22)
In order to prepare organoantimony derivatives of
sterically hindered oximes, we studied the reaction of
pentaphenylantimony with cyclohexanone oxime con-
taining a cyclohexenyl substituent in the ortho-position
and with benzyl monooxime, which also contains sev-
eral potential coordination sites.
C(31)
C(21)
C(32)
C(42)
Sb
C(51)
C(43)
C(56)
C(41)
C(52)
C(44)
RESULTS AND DISCUSSION
C(53)
It was shown that reactions of pentaphenylantimony
carried out in toluene at room temperature were com-
plete in 24 h (the course of the reactions was monitored
by TLC). The only organoantimony compound thus
formed was tetraphenylantimony oximate, which was
isolated from the reaction mixture in a yield of up to
99%
O
C(46)
C(55)
C(54)
C(45)
N
C(1)
C(11)
C(10)
C(12)
C(6)
C(7)
C(5)
Ph5Sb + HON=CRR'
Ph4SbON=CRR' + PhH,
C(2)
C(9)
C(8)
C(3)
CRR' = C6H9–C6H9-2 (I);
C(4)
R = Ph, R' = C(O)Ph (II).
According to X-ray diffraction data, the antimony
atoms in compounds I and II have a trigonal-bipyrami-
Fig. 1. Structure of molecule I.
1070-3284/04/3008-0559 © 2004 åÄIä “Nauka /Interperiodica”

560
SHARUTIN et al.
C(65)
C(64)
C(66)
C(13)
C(15)
C(14)
C(11)
O(2)
C(63)
C(16)
C(2)
C(61)
C(62)
C(12)
C(1)
O(1)
N
C(21)
C(22)
Sb
C(26)
C(32)
C(51)
C(23)
C(24)
C(42)
C(41)
C(56)
C(55)
C(52)
C(25)
C(31)
C(33)
C(46)
C(45)
C(43)
C(53)
C(54)
C(34)
C(44)
C(36)
C(35)
Fig. 2. Structure of molecule II.
angles in structures I and II lie in the ranges of torial angles is substantial, being comparable to that
84.0(1)°–85.5(1)° and 82.71(6)°–87.60(6)°, respec- observed in the structures of tetraarylantimony dicar-
tively. The deviations of the Sb atoms from the equato- boxylates in which the intramolecular Sb···O=C con-
rial plane are 0.189 and 0.178 Å in I and II, respectively. tacts result in an increase in one equatorial angle to
The sums of the CSbC angles in equatorial planes are 143.8°–151.7° [6–12].
357.7° in I and 357.9° in II. The angles between the
equatorial aryl ligands are nonequivalent, being equal
EXPERIMENTAL
to 111.4(2)°, 114.7(2)°, and 131.6(2)° in I and
113.68(7)°, 121.31(8)°, and 122.92(7)° in II. The Sb–
Ceq bond lengths (2.120(4)–2.146(4) Å in I and
2.122(2)–2.125(2) Å in II) do not differ much from the
Sb–O bond lengths (2.120(2) Å in I and 2.166(1) Å in II).
Synthesis of tetraphenylantimony 2-(cyclohexe-
nyl-1)cyclohexanone oximate (I). A mixture of pen-
taphenylantimony (0.50 g) and 2-(cyclohexenyl-
1)cyclohexanone oxime (0.19 g) in 15 ml of toluene
was kept for 24 h at 20°ë. The solvent was removed and
the residue was recrystallized from a toluene–heptane
(2 : 1 v/v) mixture. The yield of compound I was 0.61 g
(99%), mp = 148°C.
The O–N and N–C distances in compounds I and II
are equal to 1.405(4), 1.256(4) and 1.382(2), 1.280(2) Å,
respectively, which almost coincides with the lengths
of similar bonds in other tetraarylantimony oximates
[1–4]. The SbON angles are 103.6(2)° in I and
108.63(9)° in II.
It is noteworthy that the geometric parameters of the
structures of I and II differ, which suggests the influ-
ence of the nature of organic groups present in the oxi-
mate ligands at the antimony atom.
Synthesis of tetraphenylantimony 1,2-diphenyl-
ethanedione monooximate (II). A mixture of pen-
taphenylantimony (0.50 g) and benzyl monooxime
(0.22 g) in 15 ml of toluene was kept for 24 h at 20°ë.
The solvent was removed and the residue was recrystal-
lized from a toluene–heptane (2 : 1 v/v) mixture. The
yield of compound II was 0.50 g (78%), mp = 191°C.
The Sb···N distances in structures I and II
(2.806(3) Å in I and 2.918(2) Å in II) are shortened as
X-Ray diffraction analysis of the crystals of com-
compared to the sum of the van de Waals radii of the Sb pounds I and II was carried out on a SMART 1000
and N atoms (3.8 Å [5]). The intramolecular Sb···N con- CCD diffractometer (graphite monochromator, MoKα
tact in II only slightly affects the equatorial angles, radiation, λ = 0.71073 Å). The structures were solved
which differ only slightly from the ideal value (120°). by the direct method and refined by least-squares calcu-
However, in the case of I, the difference between equa- lations in the anisotropic approximation for non-hydro-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 8 2004

SYNTHESIS AND STRUCTURE OF TETRAPHENYLANTIMONY OXIMATES
Table 1. Selected bond lengths and bond angles in structures I and II
561
Bond
d, Å
Angle
ω, deg
I
Sb–O
2.120(2)
2.120(4)
2.142(4)
2.146(4)
2.203(4)
2.806(3)
1.405(4)
1.256(4)
1.506(7)
1.546(7)
1.502(7)
1.535(6)
1.548(7)
1.517(7)
OSbC(31)
85.4(1)
85.5(1)
Sb–C(31)
Sb–C(51)
Sb–C(41)
Sb–C(21)
Sb–N
OSbC(51)
C(31)SbC(51)
OSbC(41)
114.7(2)
84.0(1)
C(31)SbC(41)
C(51)SbC(41)
OSbC(21)
111.4(2)
131.6(2)
177.6(1)
97.0(2)
O–N
N–C(1)
C(31)SbC(21)
C(51)SbC(21)
C(41)SbC(21)
NOSb
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(2)–C(7)
C(3)–C(4)
C(4)–C(5)
93.2(1)
95.4(2)
103.6(2)
115.8(3)
122.8(5)
123.5(4)
C(1)NO
NC(1)C(2)
NC(1)C(6)
II
Sb–C(61)
Sb–C(41)
Sb–C(51)
Sb–O(1)
Sb–C(31)
Sb–N
2.122(2)
2.124(2)
2.125(2)
2.166(1)
2.181(2)
2.918(2)
1.280(2)
1.382(2)
1.214(2)
1.486(2)
1.517(3)
1.476(3)
1.373(3)
1.381(3)
1.383(3)
1.361(3)
1.365(3)
1.386(3)
1.372(3)
1.388(3)
1.387(4)
C(61)SbC(41)
C(61)SbC(51)
C(41)SbC(51)
C(61)SbO(1)
C(41)SbO(1)
C(51)SbO(1)
C(61)SbC(31)
C(41)SbC(31)
C(51)SbC(31)
O(1)SbC(31)
C(61)SbN
121.31(8)
122.92(7)
113.68(7)
85.32(6)
87.60(6)
82.71(6)
94.07(7)
95.58(7)
94.83(7)
176.58(6)
77.87(6)
70.83(6)
108.31(6)
26.67(4)
156.30(6)
112.5(1)
155.9(1)
44.71(7)
108.63(9)
120.2(2)
120.0(2)
N–C(1)
N–O(1)
O(2)–C(2)
C(1)–C(11)
C(1)–C(2)
C(2)–C(21)
C(41)SbN
C(11)–C(12)
C(11)–C(16)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
C(15)–C(16)
C(21)–C(26)
C(21)–C(22)
C(22)–C(23)
C(51)SbN
O(1)SbN
C(31)SbN
C(1)NO(1)
C(1)NSb
O(1)NSb
NO(1)Sb
NC(1)C(11)
NC(1)C(2)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 8 2004

562
Table 2. Crystal data and structure refinement results for I and II
Characteristics
Empirical formula
SHARUTIN et al.
I
II
C36H38NOSb
622.42
Orthorhombic
C38H30NO2Sb
M
654.38
Crystal system
Monoclinic
T, K
173(1)
298(2)
Space group
Pna21
P21/n
Unit cell parameters:
a, Å
21.599(3)
13.634(2)
10.137(2)
10.247(2)
24.380(5)
b, Å
c, Å
12.543(2)
β, deg
V, Å3
Z
90.109(4)
2985.0(8)
4
3134(1)
4
ρcalcd, g/cm3
1.385
0.953
1280
1.387
µ
Mo, mm–1
0.914
F(000)
1328
Crystal shape (size), mm
θ, deg
Prism (0.06 × 0.08 × 0.40)
2.99–24.04
Prism (0.07 × 0.24 × 0.26)
2.99–27.50
–13 ≤ h ≤ 13
–31 ≤ k ≤ 27
–13 ≤ 1 ≤ 16
20163
Ranges of reflection indices
–24 ≤ h ≤ 23
–15 ≤ k ≤ 15
–10 ≤ l ≤ 11
The total number of reflections
The number of independent reflections
The number of reflections with I > 2σ(I)
The number of refined parameters
GOOF
13943
4563 (Rint = 0.0631)
3846
7170 (Rint = 0.0449)
5349
352
379
1.067
1.034
R-factors for F2 > 2σ(F2)
R1 = 0.0414, wR2 = 0.0750
R1 = 0.0556, wR2 = 0.0791
–0.956/0.735
R1 = 0.0345, wR2 = 0.0797
R1 = 0.0535, wR2 = 0.0876
–0.378/0.502
R-factors for all reflections
The residual electron density (min/max),
e/Å3
gen atoms. The H atoms were located geometrically and the structure solution and refinement were carried out
included in the refinement according to the rider model.
The data collection and editing and the refinement of unit
cell parameters were carried out using SMART and
using the SHELXTL/PC program package [14].
The crystal data and the results of refinement for
SAINT Plus program packages [13]. All calculations for structures I and II are listed in Table 2 and the coordi-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 8 2004

SYNTHESIS AND STRUCTURE OF TETRAPHENYLANTIMONY OXIMATES
563
Table 3. Atomic coordinates (×104) and isotropic equivalent thermal parameters Ueq (×103) for structures I and II
Atom
x
y
z
Ueq, Å2
I
Sb
6640.34(9)
6639(1)
6429(1)
6246(2)
5975(2)
5364(2)
5401(3)
5637(2)
6257(2)
5943(2)
6310(2)
6320(2)
5763(2)
5616(2)
5472(2)
6626(2)
7080(2)
7051(2)
6572(2)
6128(2)
6152(2)
6885(2)
6829(2)
7004(2)
7232(2)
7290(2)
7122(2)
7433(2)
7982(2)
8503(2)
8479(2)
7933(2)
7411(2)
5669(2)
5373(2)
4747(2)
4413(2)
4707(2)
5340(2)
9496.4(1)
8037(2)
7483(2)
6630(2)
5957(4)
5544(4)
5058(4)
5801(4)
6184(3)
6449(3)
6141(3)
6581(4)
7219(3)
7850(4)
7239(3)
10990(3)
11308(3)
12244(3)
12858(3)
12550(3)
11629(3)
9896(3)
9244(3)
9513(3)
10414(3)
11091(4)
10825(3)
9018(3)
8917(3)
8585(4)
8357(3)
8463(3)
8781(3)
9282(2)
9688(3)
9526(4)
8995(4)
8606(3)
8744(3)
7903.0(5)
8624(3)
7544(3)
7804(6)
6777(5)
7214(5)
8592(6)
9585(5)
9206(5)
5416(4)
4451(5)
3102(5)
2791(6)
3976(5)
5198(5)
7077(4)
6189(4)
5640(5)
5991(5)
6868(5)
7393(4)
9857(4)
10879(4)
12151(4)
12392(4)
11381(5)
10116(4)
6802(4)
7472(4)
6839(6)
5510(6)
4837(5)
5485(4)
7590(4)
6496(5)
6319(6)
7212(6)
8319(5)
8489(5)
20.72(5)
25.6(7)
23(1)
29.6(9)
43(1)
51(2)
62(2)
57(2)
39(1)
33(1)
38(1)
49(1)
49(1)
50(2)
41(1)
24(1)
31(1)
39(1)
47(2)
39(1)
31(1)
22(1)
34(1)
41(1)
42(1)
39(1)
33(1)
23(1)
37(1)
52(2)
47(2)
43(1)
38(1)
28(1)
39(1)
54(2)
63(2)
51(2)
36(1)
O
N
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 8 2004

564
SHARUTIN et al.
Table 3. (Contd.)
Atom
x
y
z
Ueq, Å2
II
Sb
8441.9(1)
9860(1)
837.68(5)
1511(1)
1588(1)
2823(1)
1907(1)
2401(1)
1878(1)
1412(1)
1380(1)
1799(1)
2261(1)
2304(1)
2352(1)
2754(1)
2700(1)
2264(2)
1873(1)
1917(1)
112(1)
7836.3(1)
6303(1)
7322(1)
6543(1)
5999(1)
6715(1)
4953(1)
4343(2)
3375(2)
3026(2)
3635(2)
4594(2)
7605(2)
8388(2)
9221(2)
9272(2)
8502(2)
7662(2)
8415(2)
8356(2)
8753(3)
9210(2)
9301(2)
8905(2)
7345(2)
6608(2)
6310(2)
6770(2)
7504(3)
7788(2)
9363(2)
10164(2)
11179(2)
11418(2)
10632(2)
9614(2)
6731(2)
6025(2)
5345(3)
5384(2)
6082(3)
6755(2)
43.61(3)
N
48.0(4)
50.3(3)
66.5(4)
40.1(4)
46.0(5)
41.9(4)
77.5(7)
94.6(8)
69.8(7)
57.6(6)
51.0(5)
52.5(5)
78.1(7)
105.0(10)
111.5(11)
100.2(10)
73.2(7)
48.0(5)
98.7(9)
118.4(11)
78.7(8)
67.3(7)
57.1(6)
47.0(5)
76.9(8)
92.7(9)
90.6(9)
110.9(11)
87.0(8)
47.5(5)
73.4(7)
87.6(8)
77.0(8)
65.4(6)
54.4(5)
49.1(5)
77.0(8)
95.3(10)
95.8(9)
106.3(11)
80.2(8)
O(1)
9382(1)
O(2)
10197(2)
10591(2)
10790(2)
11268(2)
11183(2)
11822(3)
12589(2)
12700(2)
12038(2)
11728(2)
11776(2)
12658(3)
13476(3)
13441(3)
12573(2)
7420(2)
C(1)
C(2)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
6079(2)
66(1)
5431(2)
–386(1)
–803(1)
–765(1)
–314(1)
413(1)
6094(3)
7405(2)
8072(2)
10148(2)
10123(2)
11262(2)
12406(2)
12442(3)
11314(2)
8615(2)
0(1)
–262(1)
–115(1)
284(1)
552(1)
1208(1)
1073(1)
1285(1)
1613(1)
1751(1)
1562(1)
1050(1)
667(1)
7742(2)
7900(3)
8936(3)
9806(2)
9644(2)
6955(2)
6451(2)
5433(3)
801(1)
4893(3)
1314(1)
1681(1)
1560(1)
5361(3)
6402(2)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 8 2004

SYNTHESIS AND STRUCTURE OF TETRAPHENYLANTIMONY OXIMATES
565
8. Sharutina, O.K., Sharutin, V.V., Senchurin, V.S., et al.,
Izv. Ross. Akad. Nauk., Ser. Khim., 1996, no. 1, p. 194.
nates and thermal factors of the atoms are given in
Table 3.
9. Ferguson, G. and Kaitner, B., J. Organomet. Chem.,
1991, vol. 419, no. 2, p. 283.
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