Synthesis and structure of Sb-containing compounds of binuclear phenols

Article abstract of DOI:10.1023/A:1021198513120

The toluene solvate of 1-(tetraphenylstiboxy)-3-oxybenzene (I) was synthesized by reacting pentaphenylantimony with resorcin (at a molar ratio of 1:1) in toluene at 20°C, and the 1:3 complex (II) of 1,4- bis(tetraphenylstiboxy)benzene with hydroquinone was synthesized by reacting pentaphenylantimony with hydroquinone (at a molar ratio of 1:2) under similar conditions. The structures of the compounds obtained were determined using X-ray diffraction analysis. The Sb atoms in I and II have a distorted trigonal-bipyramidal coordination to the axial phenolate groups.

Full text of DOI:10.1023/A:1021198513120

Russian Journal of Coordination Chemistry, Vol. 28, No. 11, 2002, pp. 761–766. Translated from Koordinatsionnaya Khimiya, Vol. 28, No. 11, 2002, pp. 812–817.
Original Russian Text Copyright © 2002 by Sharutin, Pakusina, Sharutina, Subacheva, Bukvetskii, Popov, Gerasimenko.
Synthesis and Structure of Sb-Containing Compounds
of Binuclear Phenols
V. V. Sharutin, A. P. Pakusina, O. K. Sharutina, O. V. Subacheva, B. V. Bukvetskii,
D. Yu. Popov, and A. V. Gerasimenko
Blagoveshchensk Pedagogical State University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
Received June 21, 2001
Abstract—The toluene solvate of 1-(tetraphenylstiboxy)-3-oxybenzene (I) was synthesized by reacting pen-
taphenylantimony with resorcin (at a molar ratio of 1 : 1) in toluene at 20°C, and the 1 : 3 complex (II)of
1,4-bis(tetraphenylstiboxy)benzene with hydroquinone was synthesized by reacting pentaphenylantimony with
hydroquinone (at a molar ratio of 1 : 2) under similar conditions. The structures of the compounds obtained
were determined using X-ray diffraction analysis. The Sb atoms in I and II have a distorted trigonal-bipyrami-
dal coordination to the axial phenolate groups.
The syntheses of organoantimony derivatives of
In this work, the synthesis of antimony-containing
binuclear phenols from triphenylstibine (Ph3Sb) and derivatives of binuclear phenols, namely, resorcin and
substituted o-benzoquinones or from triphenylanti- hydroquinone, and their molecular and crystal struc-
mony dihalides and o-substituted phenols were tures are described.
described in [1, 2]. These compounds can be obtained
from triphenylantimony dichloride (Ph3SbCl2) and
sodium salt of cathechol derivatives [3]. A promising
method of synthesis of triphenylantimony aroxides
from Ph3Sb, binuclear phenol, and tert-buthyl hydro-
RESULTS AND DISCUSSION
It was established that reaction of pentaphenylanti-
peroxide via the reaction of oxidative addition was mony with resorcin and hydroquinone in toluene is
reported in [4].
accompanied by the replacement of one or two hydro-
C(23)
C(24)
C(25)
C(33)
C(22)
C(21)
C(14)
C(63)
C(15)
C(62)
C(61)
C(16)
C(32)
C(31)
C(13)
C(64)
C(26)
C(36)
C(12)
C(34)
C(35)
C(11)
C(1)
Sb
C(66)
C(41)
C(46)
C(65)
O(1)
C(51)
C(42)
C(56)
C(45)
C(55)
O(2)
C(43)
C(44)
C(52)
C(54)
C(53)
Fig. 1. Structure of complex I.
1070-3284/02/2811-0761$27.00 © 2002 åÄIä “Nauka /Interperiodica”

762
SHARUTIN et al.
C(15)
C(23)
C(24)
C(14)
C(13)
C(16)
C(22)
C(21)
C(11)
C(25)
C(52)
C(43)
C(44)
O(1)
C(12)
C(41)
C(42)
C(46)
C(26)
C(51)
Sb
C(53)
C(45)
C(31)
C(36)
C(35)
C(32)
C(33)
C(34)
Fig. 2. Structure of 1,4-(Ph SbO) C H in II.
4
2
6
4
C(62)
C(63)
C(64)
O(2)
O(3)
C(65)
C(61)
C(66)
C(72)
O(1)
O(4)'
C(73)
C(71)
O(4)
O(1)'
Fig. 3. A fragment of crystal structure II.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 11 2002

SYNTHESIS AND STRUCTURE OF Sb-CONTAINING COMPOUNDS
763
Table 1. Crystallographic data and details of data collection and refinement of structures I and II
Value
Parameter
I
II
C72H62O8Sb2
Empirical formula
C37H33O2Sb
633.40
M
11298.72
T, K
296(2)
293(2)
Wave length, Å
MoKα (0.71073)
Monoclinic
P21/c
MoKα (0.71073)
Symmetry
Triclinic
Space group
P1
a, Å
10.2970(9)
10.066(1)
b, Å
28.436(3)
10.244(1)
c, Å
10.3228(9)
14.833(2)
α, deg
90
83.205(2)
β, deg
94.865(2)
87.309(3)
γ, deg
90
76.956(2)
V, Å3
3011.6(5)
1479.2(4)
Z
4
1
ρ(calcd), g/cm3
1.397
1.458
µ, mm–1
0.947
1296
0.971
660
F(000)
Crystal size (shape), mm
Range of data collection for θ, deg
Ranges of reflection indices
Measured reflections
Independent reflections
Reflections with I > 2σ(I)
Method of refinement
Number of refinement variables
GOOF
Prism (0.45 × 0.45 × 0.45 mm)
2.11–28.11
Prism (0.20 × 0.25 × 0.30 mm)
2.05–25.02
–13 ≤ h ≤ 13, –37 ≤ k ≤ 33, –13 ≤ l ≤ 10 –11 ≤ h ≤ 11, –12 ≤ k ≤ 12, –16 ≤ l ≤ 17
18836
7318 (Rint = 0.0309)
5875
11578
5192 (Rint = 0.0336)
4342
Full-matrix least-squares method for F2 Full-matrix least-squares method for F2
366
373
1.019
1.019
R factors for F2 > 2σ(F2)
R factors for all reflections
Residual electron density (min/max), e/Å3
R1 = 0.0317, wR2 = 0.0798
R1 = 0.0419, wR2 = 0.0834
–0.697/0.729
R1 = 0.0360, wR2 = 0.0850
R1 = 0.0457, wR2 = 0.0888
–576/1.342 (in the neighborhood of the Sb)
gen atoms of the initial phenol by the Ph4Sb group,
The structures of the solvate of 1-(tetraphenylstib-
oxy)-3-oxybenzene Ph4SbOC6H4(OH)-3 with toluene
(I) and the 1,4-bis(tetraphenylstiboxy)benzene com-
plex with hydroquinone 1,4-(Ph4SbO)2C6H4
3C6H4(HO)2 (II) were determined using X-ray diffrac-
tion analysis (Fig. 1).
respectively:
Ph5Sb + 1,3-(HO)2C6H4
Ph4SbOC6H4(OH)-3 + PhH,
·
The antimony-containing molecule in II contains
two similar fragments joined by a twofold axis passing
through the center of the hydroquinone group and
bound to the Sb atoms through the ë(52)–ë(52‡) and
2Ph5Sb + 4C6H4(HO)2-1,4
1,4-(Ph4SbO)2C6H4 · 3C6H4(Oç)2-1,4 + 2PhH.
These reactions start even at room temperature; ë(53)–ë(53‡) bonds (Fig. 2). In crystal II, the hydro-
however, for their termination, the reaction mixture quinone molecules join molecules of 1,4-bis(tetraphen-
must be heated at 90–100°ë for 1 h.
ylstiboxy)benzene via hydrogen bonds (Fig. 3).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 11 2002

764
SHARUTIN et al.
Table 2. Coordinates of atoms (×104) and their equivalent isotropic thermal parameters (×103) in structures I and II
Atom
x
y
z
Ueq, Å2
Atom
x
y
z
Ueq, Å2
I
II
9877.3(2) 7243.9(1) 39.73(5)
Sb
8447.7(1)
910.06(5) 7966.5(1)
37.16(6) Sb
1802.9(2)
776(2)
O(1)
9085(2) 16426(5)
8072(2) 26424(8)
6846(2) 10987(9)
7719(1)
4109(2)
6643(2)
6813(3)
5963(4)
4948(4)
4759(4)
5620(3)
8179(2)
8349(3)
8450(3)
8368(3)
8194(3)
8120(3)
9987(2)
10847(3)
12171(3)
12629(3)
11780(3)
44.0(4) O(1)
62.1(5) O(2)
43.8(5) O(3)
56.2(6) O(4)
72.6(9) C(11)
80.0(1) C(12)
11188(2)
3486(4)
4940(3)
3248(2)
11727(2)
11793(3)
12949(3)
14043(3)
14002(3)
12842(3)
9197(2)
10052(3)
9565(3)
8234(3)
7372(3)
7851(3)
9069(2)
7789(3)
7299(3)
8080(4)
9329(3)
9840(3)
8706(2)
8773(3)
8156(3)
7448(3)
7389(3)
8009(3)
10569(2)
10322(3)
10225(3)
4504(3)
5178(3)
4834(3)
3834(4)
3192(4)
3528(3)
4093(2)
5125(3)
3984(3)
2620(30)
8327(1)
7383(2)
7866(2)
8966(1)
6413(2)
5516(2)
4950(2)
5242(2)
6114(2)
6703(2)
8149(2)
8386(2)
8924(2)
9249(2)
9026(2)
8461(2)
7313(2)
7715(2)
7721(2)
7325(2)
6919(2)
6914(2)
6159(2)
5914(2)
5202(2)
4702(2)
4914(2)
5641(2)
9139(2)
9887(2)
9276(2)
7769(2)
7084(2)
6972(3)
7540(2)
8232(3)
8344(2)
9478(2)
9810(2)
9685(2)
8760(20)
45(1)
122(1)
106(1)
57(1)
41(1)
54(1)
64(1)
68(1)
72(1)
63(1)
43(1)
54(1)
61(1)
69(1)
80(1)
67(1)
43(1)
65(1)
79(1)
74(1)
67(1)
56(1)
45(1)
57(1)
70(1)
77(1)
74(1)
60(1)
37(1)
45(1)
45(1)
60(1)
77(1)
84(1)
76(1)
83(1)
73(1)
43(1)
52(1)
51(1)
70
O(2)
8717(3)
3159(3)
1751(2)
1649(2)
1274(3)
1191(3)
1510(3)
1905(3)
1954(3)
3430(2)
4203(3)
5323(3)
5670(3)
4908(4)
3795(3)
45(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(1)
6086(3)
5005(3)
4686(4)
5437(4)
6501(3)
7630(2)
6309(3)
5741(3)
6475(4)
7766(4)
8439(3)
8636(2)
8069(3)
8172(4)
8855(4)
9478(3)
9373(3)
10220(2)
11283(3)
12468(3)
12609(4)
11574(4)
10361(3)
9454(2)
10721(2)
11096(3)
10250(3)
8985(2)
8587(2)
1492(1)
1580(1)
1283(1)
892(1)
79(1)
C(13)
796(1)
61.7(7) C(14)
43.0(5) C(15)
57.2(7) C(16)
68.7(8) C(21)
70.1(9) C(22)
68.4(8) C(23)
54.7(7) C(24)
40.0(5) C(25)
65.1(8) C(26)
205.8(8)
161(1)
–275(1)
–675(1)
–639(1)
–199(1)
1074.8(8)
783(1)
885(1)
82(1)
C(31)
1269(1)
1549(1)
72.0(9) C(32)
65.9(8) C(33)
53.7(6) C(34)
42.3(5) C(35)
63.5(7) C(36)
49(3)
–1142(4)
–2297(3)
–2290(3)
–1134(3)
2847(2)
4176(3)
4851(3)
4193(4)
2864(4)
2199(3)
407(2)
1450.7(9) 10469(2)
689.3(8)
626(1)
7271(2)
8159(3)
7760(4)
6497(4)
5594(4)
5978(3)
6613(2)
6258(3)
5186(3)
4447(2)
4791(2)
5858(2)
4402(7)
5521(6)
6420(8)
7549(8)
7829(7)
6939(8)
5782(7)
484(1)
82(1)
81(1)
83(1)
C(41)
C(42)
C(43)
410(1)
461(1)
603(1)
63.2(8) C(44)
38.7(5) C(45)
49.5(6) C(46)
55.1(7) C(51)
47.7(6) C(52)
43.2(5) C(53)
42.3(5) C(61)
1843.0(7)
1799.4(9)
2038(1)
2323.3(9)
2368.8(8)
2125.4(8)
1251(2)
–850(3)
4508(3)
5133(4)
6520(4)
7290(3)
6639(4)
5252(3)
862(3)
3360(10) 3337(2)
262(6)
127(2)
115(2)
145(2)
134(2)
129(2)
123(2)
C(62)
C(63)
C(64)
C(65)
C(66)
C(71)
C(72)
C(73)
H(1)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
3942(8)
3172(5)
3752(7)
5058(7)
5807(5)
5272(5)
3138(2)
2958(2)
2769(2)
2751(2)
2945(2)
3144(2)
1315(3)
–470(3)
1470(30)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 11 2002

SYNTHESIS AND STRUCTURE OF Sb-CONTAINING COMPOUNDS
Table 3. Separate bond lengths and angles in structures I and II
765
Bond
d, Å
Angle
ω, deg
I
Sb–C(41)
Sb–C(11)
Sb–C(31)
Sb–C(21)
Sb–O(1)
2.113(2)
2.120(2)
2.130(2)
2.191(2)
2.205(1)
1.359(3)
1.368(3)
C(41)SbC(11)
C(41)SbC(31)
C(11)SbC(31)
C(41)SbC(21)
C(11)SbC(21)
C(31)SbC(21)
C(41)SbO(1)
C(11)SbO(1)
C(31)SbO(1)
C(21)SbO(1)
C(51)O(1)Sb
120.2(1)
112.86(9)
125.22(9)
96.48(9)
90.65(9)
96.14(9)
88.12(8)
84.80(8)
84.39(7)
174.73(8)
126.9(1)
O(1)–C(51)
O(2)–C(55)
II
Sb–C(21)
2.107(2)
2.110(3)
2.114(2)
2.205(3)
2.276(2)
1.370(3)
1.415(4)
1.337(4)
1.367(3)
1.368(4)
1.389(4)
1.357(4)
1.355(5)
C(21)SbC(31)
C(21)SbC(11)
C(31)SbC(11)
C(21)SbC(41)
C(31)SbC(41)
C(11)SbC(41)
C(21)SbO(1)
C(31)SbO(1)
C(11)SbO(1)
C(41)SbO(1)
C(51)O(1)Sb
C(61)O(3)O(4)
C(71)O(4)O(3)
123.5(1)
119.7(1)
115.29(9)
94.03(9)
95.8(1)
Sb–C(31)
Sb–C(11)
Sb–C(41)
Sb–O(1)
O(1)–C(51)
O(2)–C(64)
O(3)–C(61)
O(4)–C(71)
C(11)–C(16)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
92.41(9)
86.10(8)
86.90(8)
84.66(8)
176.69(8)
118.5(1)
117.2(2)
104.7(2)
The antimony atoms in compounds I and II are lates. In our opinion, this is due to hydrogen bonds
coordinated to the axial oxygen atoms to form a virtu-
ally undistorted trigonal bipyramid. The sums of bond
angles in the equatorial planes are equal to 358.28(9)°
(I) and 358.49(9)° (II), and the axial OSbC angles are
equal to 174.73(8)° (I) and 176.69(8)° (II). The bond
angles between the axial and equatorial substituents in
structures I and II vary from 84.39(7)° to 96.48(9)°
(OaxSbCeq < 90°, CaxSbCeq > 90°).
O(4)–ç(1)···é(1)' between this O atom and the hydroxo
group of a free hydroquinone molecule (O···O
2.795(3), O–H 0.85(3), O···ç 1.94(3) Å; OHO angle,
178°) and the distribution of the electron density among
a larger number of bonds. Location of the hydrogen
atoms at O(2) and O(3) failed; however, the é(3)···é(4)
(2.809(3) Å) and é(2)···é(1) (3.015(3) Å) distances
indicate their weak interaction.
The equatorial Sb–C bond lengths are equal to
2.113(2)–2.130(2) Å (I) and 2.107(2)–2.114(2) Å (II).
The lengths of the Sb–Cax bonds in I and II (2.191(2)
and 2.205(3) Å) are greater than the statistically aver-
aged lengths for structurally characterized aroxytet-
raphenylantimony compounds (2.184 Å) [5]. In I, the
Sb–Oax distance (2.205(1) Å) is slightly longer than
Sb–Cax and close to the Sb–O distances in other tet-
raphenylantimony phenolates (2.121(4)–2.221(4) Å)
[5–8].
EXPERIMENTAL
Synthesis of 1-(tetraphenylstiboxy)-3-oxyben-
zene with toluene (I). A mixture of Ph5Sb (1.00 g,
1.97 mmol), resorcin (0.22 g, 1.97 mmol), and toluene
(15 ml) was heated at 100°ë for 1 h and then cooled to
room temperature; 5 ml of petroleum ether was then
added, and the mixture obtained was cooled to –18°ë.
The crystals formed were filtered off and dried. The
In II, the Sb–O bond (2.276(2) Å) is longer than the
analogous bonds in known tetraphenylantimony pheno- yield was 1.05 g (85%), mp = 159°C.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 11 2002

766
SHARUTIN et al.
The complex of 1,4-bis(tetraphenylstiboxy)ben-
ACKNOWLEDGMENTS
zene with hydroquinone (II) was synthesized as
above. The yield was 75%, mp = 105°C.
The license to use the Cambridge Structural Data-
base was supported by the Russian Foundation for
Basic Research, project no. 99-07-90133.
X-ray diffraction analysis of the natural-faceted
single crystals of compounds I and II was carried out
on a Bruker SMART-1000 CCD diffractometer. The
data were collected in sets of 606 and 606, 435, and 230
scans at ϕ = 0°, 90°, 180°, and 270°C and ϕ = 0°, 90°,
and 180°, respectively (ω-scan mode with a step of 0.3°
and a counting time of 10 s for crystal I and 20 s for
crystal II; crystal–detector distance 45 mm). Correc-
tion for absorption of X-rays by the samples was
applied using the face indices.
REFERENCES
1. Holmes, R.R., Day, R.O., Chandrasekhar, V., and
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et al., Izv. Akad. Nauk SSSR, Ser. Khim., 1980, no. 6,
p. 1446.
The structures were solved by the direct methods
and refined by the least-squares method in anisotropic
approximation for non-hydrogen atoms. The positions
of the hydrogen atoms were calculated geometrically
and refined in the rider model.
4. Dodonov, V.A., Fedorov, A.Yu., Usyatinskii, R.I., et al.,
Izv. Russ. Akad. Nauk, Ser. Khim., 1995, no. 4, p. 748.
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tion Software, Madison: Bruker AXS Inc., 1998.
10. Sheldrick, G.M., SHELXTL, Versions 5.10: An Inte-
grated System for Solving, Refining and Displaying
Crystal Structures from Diffraction Data, Madison:
Bruker AXS Inc., 1998.
The data collection and processing and the refine-
ment of the unit cell parameters were performed using
the SMART and SAINT Plus programs [9]. All the cal-
culations for the determination and the refinement of
structures I and II were carried out using the
SHELXTL/PC programs [10].
Selected crystallographic parameters and the details
of the structure refinement are presented in Table 1,
coordinates and thermal parameters of atoms are given
in Table 2, and their bond lengths and angles are listed
in Table 3.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 11 2002