Structural characterization of some novel oxidation products of triphenylstibine

Article abstract of DOI:10.1071/C96042

Room-temperature single-crystal X-ray structural characterizations of two oxidation products of triphenylstibine of the form XPh₃SbOSbPh₃X are recorded for X = Cl, NO₃. ClPh₃SbOSbPh₃Cl is monoclinic, P2₁/c, Z = 4 f.u., a 9.109(4), b 19.809(8), c 19.30(2) A, β 109.27(5)°, conventional R on |F| being 0.038 for N_o 4431 'observed' (I > 3σ(I)) independent reflections. In this complex, Sb-O-Sb is quasi-linear, 173.1(3)°, in contrast to the previously recorded benzene solvate, in which it is 139.0(3)°; in the nitrate, [(O₂NO)Ph₃SbOSbPh₃(ONO₂)], triclinic, P1, Z = 2 f.u., a 15.609(5), b 13.238(4), c 10.140(2) A, α 87.11(2), β 88.46(7), γ 72.93(2)°, R 0.036 for N_o 5275, it is also bent (137.0(2)°). The anionic substituent is opposed to the oxo bridge in the trigonal bipyramidal five-coordinate array about the metal in both complexes. A redetermination of the structure of Ph₈Sb₄O₆ is recorded, presenting a non-disordered model in a triclinic P1 cell, a 19.698(3), b 11.635(2), c 9.739(2) A, α 92.28(1), β 98.98(1), γ 99.74(1)°, Z = 2 f.u., R 0.046 for N_o 3578. A new ('β') phase of triphenylstibine, crystallized from hexane/toluene is also recorded: monoclinic, P2₁/c, a 15.386(8), b 11.304(5), c 19.078(8) A, β 111.64(4)°, Z = 8, R 0.045 for N_o 3393.

Full text of DOI:10.1071/C96042

C S I R O P U B L I S H I N G
Australian Journal
of Chemistry
Volume 50, 1997
© CSIRO Australia 1997
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Aust. J. Chem., 1997, 50, 675–681
Structural Characterization of Some Novel
Oxidation Products of Triphenylstibine
Eꢀendy,A,B Warren J. Grigsby,C Robert D. Hart,A
Colin L. Raston,C Brian W. Skelton A and Allan H. White A
A
Department of Chemistry, University of Western Australia,
Nedlands, W.A. 6907.
B
Jurusan Pendidikan Kimia, FPMIPA IKIP Malang,
Jalan Surabaya 6, Malang 65145, Indonesia.
C
Department of Chemistry, Monash University, Clayton, Vic. 3168.
Room-temperature single-crystal X-ray structural characterizations of two oxidation products of
triphenylstibine of the form XPh3SbOSbPh3X are recorded for X = Cl, NO3. ClPh3SbOSbPh3Cl is
ꢀ
ꢀ
monoclinic, P 21/c, Z = 4 f.u., a 9ꢀ109(4), b 19ꢀ809(8), c 19ꢀ30(2) A, ꢀ 109ꢀ27(5) , conventional R on
|F| being 0ꢀ038 for N o 4431 ‘observed’ (I > 3ꢁ(I)) independent reꢁections. In this complex, Sb–O–Sb is
quasi-linear, 173ꢀ1(3)ꢀ, in contrast to the previously recorded benzene solvate, in which it is 139ꢀ0(3)ꢀ;
in the nitrate, [(O2NO)Ph3SbOSbPh3(ONO2)], triclinic, P 1, Z = 2 f.u., a 15ꢀ609(5), b 13ꢀ238(4),
ꢀ
c 10ꢀ140(2) A, ꢂ 87ꢀ11(2), ꢀ 88ꢀ46(7), ꢃ 72ꢀ93(2) , R 0ꢀ036 for N o 5275, it is also bent (137ꢀ0(2)ꢀ).
The anionic substituent is opposed to the oxo bridge in the trigonal bipyramidal ꢂve-coordinate array
about the metal in both complexes. A redetermination of the structure of Ph8Sb4O6 is recorded,
ꢀ
ꢀ
presenting a non-disordered model in a triclinic P 1 cell, a 19ꢀ698(3), b 11ꢀ635(2), c 9ꢀ739(2) A,
ꢂ 92ꢀ28(1), ꢀ 98ꢀ98(1), ꢃ 99ꢀ74(1)ꢀ, Z = 2 f.u., R 0ꢀ046 for N o 3578. A new (‘ꢀ’) phase of
triphenylstibine, crystallized from hexane/toluene is also recorded: monoclinic, P 21/c, a 15ꢀ386(8),
ꢀ
ꢀ
b 11ꢀ304(5), c 19ꢀ078(8) A, ꢀ 111ꢀ64(4) , Z = 8, R 0ꢀ045 for N o 3393.
Introduction
present eꢃectively deꢂnitive level of characterization
and we report this work hereunder. The compounds in
question are (1) OSb2Ph6Cl2, obtained from silver(I)
chloride/triphenylstibine in 1 : 3 ratio in acetonitrile
solution, and (2) OSb2Ph6(NO3)2, obtained from cop-
per(I) nitrate/triphenylstibine in 1 : 3 ratio in toluene
solution, as the toluene monosolvate.
In accompanying papers1–3 we describe syntheses
and structural characterizations of adducts of triph-
enylstibine, Ph3Sb (= L), with coinage metal(I) salts,
MX, of formulation LnMX for high n (n = 3, 4) and
in which X may (n < 4) or may not (n = 4) be coordi-
nated to the metal atom, the adducts having normally
been successfully obtained by recrystallization from
an appropriate supporting solvent (e.g. acetonitrile,
pyridine). In the course of a number of these attempts,
usually after abnormally extended standing at room
temperature, small deposits of materials other than
the desired products (and diꢃering from the starting
materials) have sometimes been obtained, these being
characterized by room-temperature single-crystal X-ray
studies with substantial certainty, given their history,
as oxidation products of triphenylstibine, of the form
X(Ph3Sb)O(SbPh3)X, in particular for X = Cl, NO3,
with the antimony pentavalent. As these studies fall
outside the main thrust of our study we have not further
pursued the mode of formation (oxidation by the metal,
air, anion, etc.); nevertheless, the compounds are of
suꢄcient novelty and interest to justify recording at the
The chloride is of particular interest; it has been
the subject of a previous determination as a benzene
disolvate.4 The two determinations record radically
diꢃerent results in respect of the linearity or otherwise
at the central oxygen. Curiously, a contemporary
record of determinations of two diꢃerent phases of the
iodide has also been reported,5 displaying a similar
discrepancy and oꢃering a basis for comparison.
We also take the opportunity to record a redeter-
mination of tetranuclear Ph8Sb4O6, deposited from
a copper(I) perchlorate/triphenylstibine reaction mix-
ture in 1 : 4 ratio in acetonitrile solution. We think
there is good reason to believe the present form of
the compound to be the same as that for which a
structure determination has been previously recorded
in a cell of half the size6 with a totally disordered
reꢂnement model; the present model in the present
Manuscript received 7 March 1996
0004-9425/97/060675$05.00
10.1071/CH96042

676
Short Communications
Table 1. Non-hydrogen positional and isotropic displacement
parameters for (1)
Table 2 (Continued)
ꢀ2
U/A
Atom
x
y
z
ꢀ2
Atom
x
y
z
Ueq/A
C(214)
C(215)
C(216)
C(221)
C(222)
C(223)
C(224)
C(225)
C(226)
C(231)
C(232)
C(233)
C(234)
C(235)
C(236)
C(11)
C(1)
0ꢁ9071(6)
0ꢁ9691(4)
0ꢁ9417(4)
0ꢁ6820(3)
0ꢁ6282(4)
0ꢁ5434(4)
0ꢁ5111(4)
0ꢁ5636(5)
0ꢁ6492(4)
0ꢁ9111(3)
0ꢁ9885(4)
1ꢁ0533(4)
1ꢁ0430(4)
0ꢁ9665(5)
0ꢁ9002(4)
0ꢁ5071(9)
0ꢁ5687(6)
0ꢁ5814(7)
0ꢁ6557(9)
0ꢁ7173(6)
0ꢁ7045(7)
0ꢁ6303(9)
0ꢁ6211(6)
0ꢁ6329(5)
0ꢁ6618(5)
0ꢁ7231(4)
0ꢁ8036(5)
0ꢁ8030(6)
0ꢁ7216(6)
0ꢁ6425(6)
0ꢁ6423(5)
0ꢁ7321(4)
0ꢁ6488(5)
0ꢁ6562(6)
0ꢁ7445(6)
0ꢁ8279(5)
0ꢁ8234(5)
0ꢁ604(1)
0ꢁ5377(7)
0ꢁ6249(7)
0ꢁ7526(6)
1ꢁ0386(5)
1ꢁ1112(6)
1ꢁ1520(7)
1ꢁ1211(7)
1ꢁ0463(7)
1ꢁ0074(6)
1ꢁ1124(5)
1ꢁ1279(6)
1ꢁ2135(7)
0ꢁ2839(6)
1ꢁ2678(6)
1ꢁ1819(6)
0ꢁ675(2)
0ꢁ080(3)
0ꢁ072(3)
0ꢁ058(2)
0ꢁ047(2)
0ꢁ063(3)
0ꢁ077(3)
0ꢁ073(3)
0ꢁ081(3)
0ꢁ063(3)
0ꢁ045(2)
0ꢁ056(2)
0ꢁ071(3)
0ꢁ074(3)
0ꢁ070(3)
0ꢁ057(2)
0ꢁ20(1)
Sb(1)
Sb(2)
O
Cl(1)
Cl(2)
0ꢁ59893(4)
0ꢁ84530(5)
0ꢁ7174(4)
0ꢁ4409(2)
1ꢁ0145(2)
0ꢁ7862(6)
0ꢁ8590(8)
0ꢁ9922(8)
1ꢁ0474(8)
0ꢁ9728(9)
0ꢁ8415(8)
0ꢁ4243(6)
0ꢁ3775(8)
0ꢁ2779(9)
0ꢁ2182(9)
0ꢁ2621(9)
0ꢁ3655(8)
0ꢁ5852(7)
0ꢁ4548(8)
0ꢁ450(1)
0ꢁ49864(2)
0ꢁ63291(2)
0ꢁ5641(2)
0ꢁ41832(8)
0ꢁ71362(9)
0ꢁ4798(3)
0ꢁ4183(3)
0ꢁ4070(4)
0ꢁ4558(5)
0ꢁ5161(4)
0ꢁ5298(3)
0ꢁ5708(3)
0ꢁ5881(3)
0ꢁ6410(4)
0ꢁ6745(4)
0ꢁ6571(4)
0ꢁ6055(4)
0ꢁ4293(3)
0ꢁ3894(4)
0ꢁ3454(4)
0ꢁ3386(4)
0ꢁ3777(4)
0ꢁ4236(3)
0ꢁ6544(3)
0ꢁ7194(3)
0ꢁ7334(4)
0ꢁ6823(5)
0ꢁ6164(4)
0ꢁ6023(3)
0ꢁ6967(3)
0ꢁ7395(4)
0ꢁ7782(4)
0ꢁ7735(5)
0ꢁ7299(5)
0ꢁ6914(3)
0ꢁ5606(3)
0ꢁ5464(4)
0ꢁ4943(5)
0ꢁ4597(4)
0ꢁ4755(4)
0ꢁ5261(4)
0ꢁ18024(2)
0ꢁ31853(2)
0ꢁ2541(2)
0ꢁ08123(9)
0ꢁ4151(1)
0ꢁ1417(3)
0ꢁ1572(4)
0ꢁ1387(4)
0ꢁ1048(4)
0ꢁ0891(4)
0ꢁ1070(3)
0ꢁ1354(3)
0ꢁ0625(3)
0ꢁ0380(4)
0ꢁ0831(5)
0ꢁ1559(5)
0ꢁ1825(3)
0ꢁ2611(3)
0ꢁ2504(4)
0ꢁ3040(5)
0ꢁ3672(5)
0ꢁ3780(4)
0ꢁ3242(4)
0ꢁ3641(3)
0ꢁ3748(4)
0ꢁ3994(5)
0ꢁ4147(5)
0ꢁ4049(4)
0ꢁ3783(3)
0ꢁ2335(4)
0ꢁ2431(5)
0ꢁ1826(6)
0ꢁ1162(6)
0ꢁ1065(5)
0ꢁ1661(4)
0ꢁ3606(3)
0ꢁ4337(4)
0ꢁ4579(5)
0ꢁ4108(7)
0ꢁ3378(5)
0ꢁ3127(4)
0ꢁ0454(1)
0ꢁ0487(2)
0ꢁ059(2)
0ꢁ0670(7)
0ꢁ0830(8)
0ꢁ050(2)
0ꢁ067(3)
0ꢁ084(4)
0ꢁ082(4)
0ꢁ079(3)
0ꢁ066(3)
0ꢁ052(2)
0ꢁ066(3)
0ꢁ077(3)
0ꢁ089(4)
0ꢁ094(4)
0ꢁ073(3)
0ꢁ052(2)
0ꢁ075(3)
0ꢁ094(4)
0ꢁ090(4)
0ꢁ087(4)
0ꢁ070(3)
0ꢁ049(2)
0ꢁ077(3)
0ꢁ095(4)
0ꢁ090(4)
0ꢁ082(4)
0ꢁ061(3)
0ꢁ060(3)
0ꢁ086(4)
0ꢁ107(5)
0ꢁ112(6)
0ꢁ105(5)
0ꢁ082(4)
0ꢁ055(2)
0ꢁ081(3)
0ꢁ107(5)
0ꢁ107(5)
0ꢁ097(4)
0ꢁ076(3)
C(111)
C(112)
C(113)
C(114)
C(115)
C(116)
C(121)
C(122)
C(123)
C(124)
C(125)
C(126)
C(131)
C(132)
C(133)
C(134)
C(135)
C(136)
C(211)
C(212)
C(213)
C(214)
C(215)
C(216)
C(221)
C(222)
C(223)
C(224)
C(225)
C(226)
C(231)
C(232)
C(233)
C(234)
C(235)
C(236)
0ꢁ5590(8)
0ꢁ5852(6)
0ꢁ5247(9)
0ꢁ4380(8)
0ꢁ4119(6)
0ꢁ4723(9)
0ꢁ609(1)
0ꢁ19(1)
C(2)
C(3)
C(4)
C(5)
C(6)
0ꢁ476(1)
0ꢁ148(8)
0ꢁ20(1)
0ꢁ4057(7)
0ꢁ469(1)
0ꢁ24(1)
0ꢁ602(1)
0ꢁ31(2)
0ꢁ6718(7)
0ꢁ22(1)
0ꢁ573(1)
0ꢁ702(1)
0ꢁ7073(8)
0ꢁ6693(6)
0ꢁ6324(8)
0ꢁ5107(9)
0ꢁ4278(9)
0ꢁ4632(9)
0ꢁ5840(7)
0ꢁ8625(8)
0ꢁ9835(9)
0ꢁ987(1)
0ꢁ877(1)
0ꢁ756(1)
0ꢁ747(1)
1ꢁ0227(7)
1ꢁ0784(8)
1ꢁ184(1)
1ꢁ236(1)
1ꢁ1806(9)
1ꢁ0741(8)
Table 2. Non-hydrogen positional and isotropic displacement
parameters for (2)
ꢀ2
Atom
x
y
z
U/A
Sb(1)
Sb(2)
O
0ꢁ77166(2)
0ꢁ81133(2)
0ꢁ7721(2)
0ꢁ7738(2)
0ꢁ6306(3)
0ꢁ6963(3)
0ꢁ6970(3)
0ꢁ8515(2)
0ꢁ8448(3)
0ꢁ8200(3)
0ꢁ8379(3)
0ꢁ7341(3)
0ꢁ6937(4)
0ꢁ6748(4)
0ꢁ6974(4)
0ꢁ7377(5)
0ꢁ7563(4)
0ꢁ9099(3)
0ꢁ9658(4)
1ꢁ0583(4)
1ꢁ0932(4)
1ꢁ0383(4)
0ꢁ9464(4)
0ꢁ6803(4)
0ꢁ6918(5)
0ꢁ6304(8)
0ꢁ5579(9)
0ꢁ5447(6)
0ꢁ6066(5)
0ꢁ8528(4)
0ꢁ7930(4)
0ꢁ8196(5)
0ꢁ98189(3)
0ꢁ72623(3)
0ꢁ8813(3)
1ꢁ0942(3)
1ꢁ1704(3)
1ꢁ1710(5)
1ꢁ1481(4)
0ꢁ5496(3)
0ꢁ4177(4)
0ꢁ5725(4)
0ꢁ5119(4)
1ꢁ1116(4)
1ꢁ1028(5)
1ꢁ1843(6)
1ꢁ2747(5)
1ꢁ2845(5)
1ꢁ2023(5)
0ꢁ9351(4)
0ꢁ9156(5)
0ꢁ8803(6)
0ꢁ8637(5)
0ꢁ8823(5)
0ꢁ9180(5)
0ꢁ9332(5)
0ꢁ9162(6)
0ꢁ8809(8)
0ꢁ8664(9)
0ꢁ8820(8)
0ꢁ9151(5)
0ꢁ6794(4)
0ꢁ6655(5)
0ꢁ6377(6)
0ꢁ79954(3)
0ꢁ98126(3)
0ꢁ9489(3)
0ꢁ6219(3)
0ꢁ6415(4)
0ꢁ4527(5)
0ꢁ5704(5)
1ꢁ0175(4)
1ꢁ1475(5)
1ꢁ2277(4)
1ꢁ1363(6)
0ꢁ9230(5)
1ꢁ0442(6)
1ꢁ1280(6)
1ꢁ0933(7)
0ꢁ9738(7)
0ꢁ8888(6)
0ꢁ7595(5)
0ꢁ8653(6)
0ꢁ8471(7)
0ꢁ7224(7)
0ꢁ6158(6)
0ꢁ6337(6)
0ꢁ6902(6)
0ꢁ5559(7)
0ꢁ490(1)
0ꢁ0409(1)
0ꢁ0427(1)
0ꢁ049(1)
0ꢁ054(2)
0ꢁ070(2)
0ꢁ107(3)
0ꢁ060(2)
0ꢁ055(2)
0ꢁ091(2)
0ꢁ077(2)
0ꢁ061(2)
0ꢁ042(2)
0ꢁ056(2)
0ꢁ070(3)
0ꢁ070(3)
0ꢁ073(3)
0ꢁ059(2)
0ꢁ043(2)
0ꢁ059(2)
0ꢁ071(3)
0ꢁ068(3)
0ꢁ068(3)
0ꢁ057(2)
0ꢁ059(3)
0ꢁ088(4)
0ꢁ129(6)
0ꢁ144(7)
0ꢁ123(5)
0ꢁ082(3)
0ꢁ047(2)
0ꢁ066(3)
0ꢁ076(3)
O(11)
O(12)
O(13)
N(1)
O(21)
O(22)
O(23)
N(2)
C(111)
C(112)
C(113)
C(114)
C(115)
C(116)
C(121)
C(122)
C(123)
C(124)
C(125)
C(126)
C(131)
C(132)
C(133)
C(134)
C(135)
C(136)
C(211)
C(212)
C(213)
0ꢁ555(1)
0ꢁ688(1)
0ꢁ7576(8)
0ꢁ7902(5)
0ꢁ7007(6)
0ꢁ5734(6)
Fig. 1. Projection of Cl(Ph3Sb)O(SbPh3)Cl: (a) normal to;
(b) down the Sbꢀ ꢀ ꢀSb line.

Short Communications
677
Fig. 2. Projections of [(O2NO)(Ph3Sb)O(SbPh3)(ONO2)]:
(a) normal to; (b) down the Sbꢀ ꢀ ꢀSb line.
Fig. 3. The two molecules of Ph8Sb4O6.

678
Short Communications
Table 3. Non-hydrogen positional and isotropic displacement
parameters for (3)
Table 4 (Continued)
ꢀ2
Ueq/A
Atom
x
y
z
ꢀ2
Atom
x
y
z
U/A
C(125)
C(126)
C(131)
C(132)
C(133)
C(134)
C(135)
C(136)
C(211)
C(212)
C(213)
C(214)
C(215)
C(216)
C(221)
C(222)
C(223)
C(224)
C(225)
C(226)
C(231)
C(232)
C(233)
C(234)
C(235)
C(236)
0ꢁ2874(5)
0ꢁ3270(5)
0ꢁ6098(5)
0ꢁ6313(5)
0ꢁ7199(6)
0ꢁ7910(6)
0ꢁ7750(6)
0ꢁ6856(6)
0ꢁ0748(4)
ꢂ0ꢁ0191(5)
ꢂ0ꢁ0725(5)
ꢂ0ꢁ0300(6)
0ꢁ0644(6)
0ꢁ1168(5)
0ꢁ0537(5)
0ꢁ0414(5)
ꢂ0ꢁ0268(5)
ꢂ0ꢁ0824(6)
ꢂ0ꢁ0720(6)
ꢂ0ꢁ0048(5)
0ꢁ2213(4)
0ꢁ1912(5)
0ꢁ2323(5)
0ꢁ3075(6)
0ꢁ3393(5)
0ꢁ2973(5)
0ꢁ0508(8)
0ꢁ1497(7)
0ꢁ2359(6)
0ꢁ1650(7)
0ꢁ1279(7)
0ꢁ1603(9)
0ꢁ229(1)
0ꢁ6323(5)
0ꢁ6146(4)
0ꢁ6046(4)
0ꢁ5539(4)
0ꢁ5662(4)
0ꢁ6305(5)
0ꢁ6819(5)
0ꢁ6688(4)
0ꢁ4093(3)
0ꢁ3920(4)
0ꢁ3964(4)
0ꢁ4165(4)
0ꢁ4362(4)
0ꢁ4319(4)
0ꢁ3640(4)
0ꢁ4144(4)
0ꢁ3915(4)
0ꢁ3168(5)
0ꢁ2665(4)
0ꢁ2891(4)
0ꢁ5117(4)
0ꢁ5663(4)
0ꢁ6407(4)
0ꢁ6610(4)
0ꢁ6070(5)
0ꢁ5327(5)
0ꢁ106(4)
0ꢁ091(4)
0ꢁ078(3)
0ꢁ088(4)
0ꢁ100(4)
0ꢁ116(5)
0ꢁ134(5)
0ꢁ109(4)
0ꢁ067(3)
0ꢁ078(3)
0ꢁ095(4)
0ꢁ100(4)
0ꢁ096(4)
0ꢁ080(3)
0ꢁ071(3)
0ꢁ076(3)
0ꢁ087(4)
0ꢁ101(4)
0ꢁ108(4)
0ꢁ091(4)
0ꢁ069(3)
0ꢁ077(3)
0ꢁ094(4)
0ꢁ105(4)
0ꢁ116(5)
0ꢁ092(4)
Molecule 1
Sb(1)
Sb(2)
O(1)
O(2)
O(3)
0ꢁ48015(5)
0ꢁ54245(5)
0ꢁ5823(4)
0ꢁ4609(4)
0ꢁ5449(4)
0ꢁ5309(8)
0ꢁ5888(7)
0ꢁ6178(9)
0ꢁ590(1)
0ꢁ05847(8)
ꢂ0ꢁ17868(8)
ꢂ0ꢁ1454(7)
ꢂ0ꢁ0969(7)
ꢂ0ꢁ0370(7)
0ꢁ212(1)
0ꢁ64534(9)
0ꢁ6437(1)
0ꢁ4820(9)
0ꢁ5135(9)
0ꢁ7493(8)
0ꢁ771(1)
0ꢁ741(2)
0ꢁ826(2)
0ꢁ936(2)
0ꢁ964(2)
0ꢁ883(2)
0ꢁ749(1)
0ꢁ864(1)
0ꢁ929(2)
0ꢁ873(2)
0ꢁ763(2)
0ꢁ698(1)
0ꢁ643(1)
0ꢁ664(2)
0ꢁ663(2)
0ꢁ647(2)
0ꢁ628(2)
0ꢁ628(2)
0ꢁ764(2)
0ꢁ903(2)
0ꢁ983(2)
0ꢁ922(2)
0ꢁ784(2)
0ꢁ706(2)
0ꢁ0344(4)
0ꢁ0380(4)
0ꢁ045(4)
0ꢁ040(4)
0ꢁ043(4)
0ꢁ044(6)
0ꢁ050(6)
0ꢁ073(8)
0ꢁ09(1)
0ꢁ2664(8)
0ꢁ3051(6)
0ꢁ3159(6)
0ꢁ2199(7)
0ꢁ1118(7)
0ꢁ1000(7)
0ꢁ1940(7)
0ꢁ5800(6)
0ꢁ6590(6)
0ꢁ7451(7)
0ꢁ7546(8)
0ꢁ6767(8)
0ꢁ5902(7)
0ꢁ4949(6)
0ꢁ4557(7)
0ꢁ4895(7)
0ꢁ5660(8)
0ꢁ6075(8)
0ꢁ5739(7)
C(111)
C(112)
C(113)
C(114)
C(115)
C(116)
C(121)
C(122)
C(123)
C(124)
C(125)
C(126)
C(211)
C(212)
C(213)
C(214)
C(215)
C(216)
C(221)
C(222)
C(223)
C(224)
C(225)
C(226)
0ꢁ285(1)
0ꢁ385(1)
0ꢁ417(2)
0ꢁ533(1)
0ꢁ346(2)
0ꢁ074(9)
0ꢁ059(7)
0ꢁ035(5)
0ꢁ051(6)
0ꢁ061(7)
0ꢁ060(7)
0ꢁ057(7)
0ꢁ051(6)
0ꢁ044(6)
0ꢁ057(7)
0ꢁ071(8)
0ꢁ073(8)
0ꢁ072(8)
0ꢁ051(6)
0ꢁ048(6)
0ꢁ065(8)
0ꢁ09(1)
0ꢁ5027(8)
0ꢁ3959(7)
0ꢁ4043(8)
0ꢁ3494(9)
0ꢁ2827(8)
0ꢁ2729(8)
0ꢁ3290(8)
0ꢁ4647(8)
0ꢁ4835(8)
0ꢁ434(1)
0ꢁ245(1)
ꢂ0ꢁ008(1)
ꢂ0ꢁ069(1)
ꢂ0ꢁ116(1)
ꢂ0ꢁ103(1)
ꢂ0ꢁ040(1)
0ꢁ006(1)
ꢂ0ꢁ324(1)
ꢂ0ꢁ430(1)
ꢂ0ꢁ531(1)
ꢂ0ꢁ523(1)
ꢂ0ꢁ415(2)
ꢂ0ꢁ316(1)
ꢂ0ꢁ229(1)
ꢂ0ꢁ193(1)
ꢂ0ꢁ227(2)
ꢂ0ꢁ297(2)
ꢂ0ꢁ333(2)
ꢂ0ꢁ301(1)
0ꢁ364(1)
0ꢁ3434(8)
0ꢁ3934(8)
0ꢁ6301(7)
0ꢁ6500(8)
0ꢁ707(1)
0ꢁ7438(9)
0ꢁ727(1)
0ꢁ09(1)
0ꢁ09(1)
0ꢁ6702(9)
0ꢁ067(8)
Molecule 2
Sb(1)
Sb(2)
O(1)
O(2)
O(3)
ꢂ0ꢁ06531(5)
ꢂ0ꢁ08348(5)
ꢂ0ꢁ0087(5)
ꢂ0ꢁ0073(4)
ꢂ0ꢁ1301(5)
ꢂ0ꢁ1259(7)
ꢂ0ꢁ1107(9)
ꢂ0ꢁ147(1)
ꢂ0ꢁ2011(9)
ꢂ0ꢁ2168(9)
ꢂ0ꢁ1802(9)
ꢂ0ꢁ1070(8)
ꢂ0ꢁ1705(9)
ꢂ0ꢁ193(1)
ꢂ0ꢁ159(1)
ꢂ0ꢁ099(1)
ꢂ0ꢁ0734(9)
ꢂ0ꢁ0739(8)
ꢂ0ꢁ0748(9)
ꢂ0ꢁ067(1)
ꢂ0ꢁ056(1)
ꢂ0ꢁ055(1)
ꢂ0ꢁ0629(9)
ꢂ0ꢁ1548(8)
ꢂ0ꢁ2276(8)
ꢂ0ꢁ2741(9)
ꢂ0ꢁ256(1)
ꢂ0ꢁ185(1)
ꢂ0ꢁ1367(8)
0ꢁ54540(8)
0ꢁ28823(9)
0ꢁ3300(8)
0ꢁ4126(7)
0ꢁ4154(8)
0ꢁ670(1)
0ꢁ727(2)
0ꢁ812(2)
0ꢁ837(1)
0ꢁ780(1)
0ꢁ693(1)
0ꢁ500(1)
0ꢁ425(1)
0ꢁ394(2)
0ꢁ445(2)
0ꢁ518(2)
0ꢁ548(2)
0ꢁ164(1)
0ꢁ052(2)
ꢂ0ꢁ037(2)
ꢂ0ꢁ005(2)
0ꢁ104(2)
0ꢁ192(2)
0ꢁ197(1)
0ꢁ187(1)
0ꢁ126(2)
0ꢁ071(2)
0ꢁ080(2)
0ꢁ142(1)
0ꢁ3960(1)
0ꢁ5052(1)
0ꢁ656(1)
0ꢁ4115(9)
0ꢁ462(1)
0ꢁ458(2)
0ꢁ586(2)
0ꢁ622(2)
0ꢁ525(2)
0ꢁ401(2)
0ꢁ361(2)
0ꢁ182(2)
0ꢁ141(2)
ꢂ0ꢁ004(3)
ꢂ0ꢁ104(2)
ꢂ0ꢁ061(2)
0ꢁ078(2)
0ꢁ350(2)
0ꢁ388(2)
0ꢁ289(3)
0ꢁ162(2)
0ꢁ125(2)
0ꢁ217(2)
0ꢁ617(2)
0ꢁ570(2)
0ꢁ637(2)
0ꢁ756(2)
0ꢁ802(2)
0ꢁ733(2)
0ꢁ0475(4)
0ꢁ0483(4)
0ꢁ054(4)
0ꢁ050(4)
0ꢁ060(4)
0ꢁ049(6)
0ꢁ072(8)
0ꢁ080(9)
0ꢁ065(8)
0ꢁ074(8)
0ꢁ071(8)
0ꢁ060(7)
0ꢁ071(8)
0ꢁ09(1)
C(111)
C(112)
C(113)
C(114)
C(115)
C(116)
C(121)
C(122)
C(123)
C(124)
C(125)
C(126)
C(211)
C(212)
C(213)
C(214)
C(215)
C(216)
C(221)
C(222)
C(223)
C(224)
C(225)
C(226)
0ꢁ09(1)
0ꢁ11(1)
0ꢁ09(1)
0ꢁ058(7)
0ꢁ071(8)
0ꢁ09(1)
0ꢁ09(1)
0ꢁ09(1)
0ꢁ073(8)
0ꢁ050(6)
0ꢁ063(7)
0ꢁ074(8)
0ꢁ071(8)
0ꢁ08(1)
0ꢁ066(7)
Table 4. Non-hydrogen positional and isotropic displacement
parameters for (4)
ꢀ2
Atom
x
y
z
Ueq/A
Sb(1)
Sb(2)
0ꢁ47337(4)
0ꢁ16069(4)
0ꢁ4178(5)
0ꢁ3701(5)
0ꢁ3372(5)
0ꢁ3487(5)
0ꢁ3947(5)
0ꢁ4271(5)
0ꢁ4173(5)
0ꢁ4663(5)
0ꢁ4275(5)
0ꢁ3368(6)
0ꢁ30358(4)
0ꢁ44661(5)
0ꢁ2727(6)
0ꢁ1704(6)
0ꢁ1558(7)
0ꢁ2421(7)
0ꢁ3444(8)
0ꢁ3598(6)
0ꢁ1464(6)
0ꢁ0424(6)
ꢂ0ꢁ0573(7)
ꢂ0ꢁ0513(8)
0ꢁ58651(3)
0ꢁ39522(3)
0ꢁ4671(3)
0ꢁ4347(4)
0ꢁ3571(4)
0ꢁ3119(4)
0ꢁ3417(4)
0ꢁ4190(4)
0ꢁ6165(3)
0ꢁ6372(4)
0ꢁ6545(4)
0ꢁ6518(4)
0ꢁ0835(3)
0ꢁ0776(2)
0ꢁ068(3)
0ꢁ078(3)
0ꢁ084(4)
0ꢁ088(4)
0ꢁ094(4)
0ꢁ086(4)
0ꢁ066(3)
0ꢁ080(3)
0ꢁ098(4)
0ꢁ102(4)
C(111)
C(112)
C(113)
C(114)
C(115)
C(116)
C(121)
C(122)
C(123)
C(124)
Fig. 4. The two molecules of the asymmetric unit of ‘ꢀ’-
triphenylstibine, projected pairwise with their inversion images
down the Sbꢀ ꢀ ꢀSb lines.

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679

680
Short Communications
Table 7. Pendant carbon angles and phenyl torsion angles in Ph8Sb4O6
Feature
Atoms
Angles/degrees (mols 1; 2)
Pendant carbon angles
Sb(1)–C(111)–C(112,6)
Sb(1)–C(121)–C(122,6)
Sb(2)–C(211)–C(212,6)
Sb(2)–C(221)–C(222,6)
123(1), 119(1); 122(1), 118(1)
123(1), 121(1); 121(1), 121(1)
119(1), 122(1); 117(1), 123(1)
121(1), 121(1); 120(1), 124(1)
Phenyl torsion angles
O(2)–Sb(1)–C(111)–C(112,6)
O(2)–Sb(1)–C(121)–C(122,6)
O(2)–Sb(2)–C(211)–C(212,6)
O(2)–Sb(2)–C(221)–C(222,6)
37(2), ꢁ148(1); 38(2), ꢁ144(1)
91(1), ꢁ87(1); 93(1), ꢁ90(2)
156(1), ꢁ27(1); 143(1), ꢁ33(1)
79(3), ꢁ101(3); 94(3), ꢁ87(3)
cell is well behaved. Further, we record a new phase
(‘ꢀ’) of triphenylstibine, obtained from hexane/toluene
solution.
compounds of the type XPh3SbOSbPh3X, X = halide
or pseudo-halide, viz. Cl (as benzene solvate),4 Br,7
N3,8 are summarized geometrically in company with the
present in Table 5. Also worthy of passing note is the
very recent structural record of binuclear homologues
[XPh2Sb(ꢄ-O)2/2]2.9 Geometries of the present two
systems are given in detail in Table 5; the molecules
are depicted in Figs 1 and 2. Features initially worthy of
note are the ‘staggered’ disposition of the phenyl groups
in projection down the Sbꢀ ꢀ ꢀSb line, the substantial
diꢃerences in the Sb–O–Sb angles, and the unidentate
coordination of the nitrate groups in that complex,
involving unusually lengthened N–O distances.
Of particular note is the characterization of a sec-
ond phase of the chloride and the observation of a
remarkable diꢃerence in the angles subtended at the
central oxygen atom by the two antimony atoms, these
being 139ꢀ0(3)ꢀ in the previously studied benzene
solvate4 and 173ꢀ1(3)ꢀ in the present. By a remark-
able coincidence, the results of an equally remarkable
contemporary study have just appeared, recording the
structural characterization of two polymorphs of the
iodide analogue,5 neither being isomorphous with the
present chloride. The two iodide polymorphs display
angles of 180ꢀ and 144ꢀ6(4)ꢀ at the central oxygen, the
variation in angle correlating with variations in Sb–O
Structure Determination
General procedures are given in ref. 1; speciꢁc details are
as follows (see also Tables 1–7 and Figs 1–4).
(1) [(Cl)Ph3SbOSbPh3(Cl)]. C36H30Cl2OSb2, M 793ꢀ0.
Monoclinic, space group P 21/c (C25h, No. 14), a 9ꢀ109(4),
ꢀ
ꢀ
ꢀ3
b 19ꢀ809(8), c 19ꢀ30(2) A, ꢀ 109ꢀ27(5) , V 3287 A . Dc(Z = 4
f.u.) 1ꢀ60 g cmꢁ3; F(000) 15ꢂ60. ꢁMo 16ꢀ9 cmꢁ1; specimen:
0ꢀ46 by 0ꢀ40 by 0ꢀ39 mm; Amin,max 1ꢀ66, 1ꢀ81. 2ꢂmax 50ꢀ;
N 5757, N o 4431; R 0ꢀ038, Rw 0ꢀ044.
(2) [(O2NO)Ph3SbOSbPh3(ONO2)].C7H 8. C43H38N2O7-
Sb2,
M
937ꢀ9. Triclinic, space group P 1 (Ci1, No. 2),
ꢀ
a 15ꢀ609(5), b 13ꢀ238(4), c 10ꢀ140(2) A, ꢃ 87ꢀ11(2), ꢀ 88ꢀ46(7),
ꢄ 72ꢀ93(2) , V 2001 A . Dc(Z = 2 f.u.) 1ꢀ56 g cmꢁ3; F(000)
936. ꢁMo 14ꢀ0 cmꢁ1; specimen: 0ꢀ32 by 0ꢀ14 by 1ꢀ00 mm;
Aꢂmin,max 1ꢀ20, 1ꢀ60. 2ꢂmax 50ꢀ; N 7026, N o 5275; R 0ꢀ036,
Rw 0ꢀ039.
ꢀ3
ꢀ
Variata for (2). The toluene molecule, although exhibiting
high thermal motion, reꢁned to unit population and with no
overt disorder; in ꢁnal reꢁnement cycles it was modelled as a
rigid body.
(3) Ph8Sb4O6. C48H40O6Sb4, M 1199ꢀ5. Triclinic, space
ꢀ
group P 1, a 19ꢀ698(3), b 11ꢀ635(2), c 9ꢀ739(2) A, ꢃ 92ꢀ28(1),
ꢀ
ꢀ3
ꢀ 98ꢀ98(1), ꢄ 99ꢀ74(1) , V 2168 A . Dc(Z = 2 f.u.) 1ꢀ84
g cmꢁ3; F(000) 1160. ꢁMo 25ꢀ4 cmꢁ1; specimen: 0ꢀ10 by
0ꢀ24 by 0ꢀ18 mm; Aꢂmin,max 1ꢀ15, 1ꢀ63. 2ꢂmax 45ꢀ; N 5295,
N o 3578; R 0ꢀ046, Rw 0ꢀ047.
ꢀ
(4) Ph3Sb. C18H15Sb, M 353ꢀ1. Monoclinic, space group
(1ꢀ9410(6), 1ꢀ9437(6) versus 1ꢀ986(8), 1ꢀ956(8) A) and
ꢀ
ꢀ
P 21/c, a 15ꢀ386(8), b 11ꢀ304(5), c 19ꢀ078(8) A, ꢀ 111ꢀ64(4) ,
ꢀ
Sb–I (2ꢀ954(1), 2ꢀ968(1) versus 2ꢀ991(3), 2ꢀ995(1) A);
ꢀ3
V
3084 A . Dc(Z = 8) 1ꢀ52 g cmꢁ3
; F(000) 1392. ꢁMo
counterpart values in the chloride systems for Sb–O
17ꢀ7 cmꢁ1; specimen: 0ꢀ55 by 0ꢀ20 by 0ꢀ35 mm; Aꢂmin,max
ꢀ
are 1ꢀ965(4), 1ꢀ951(4) versus 1ꢀ980(6), 1ꢀ986(6) A,
1ꢀ41, 1ꢀ84. 2ꢂmax 50ꢀ; N 5427, N o 3393; R 0ꢀ045, Rw 0ꢀ046.
supporting a similar correlation with change in angle.
In both sets of examples, the angular values of linearity
and c. 140ꢀ correspond to the dichotomy deꢂned for
such compounds by Glidewell.10
Discussion
Given the histories of the materials, the results of the
room-temperature single-crystal X-ray studies of the
ꢂrst two complexes are consistent in likely stoichiometry
and connectivity with their formulation as members
of the well known family of oxo-bridged antimony(V)
compounds X(Ph3Sb)O(SbPh3)X, two ꢂve-coordinate
antimony(V) species being bridged by an oxygen atom
lying axially trans in a quasi-trigonal bipyramidal
coordination sphere to a unidentate anion, the three
phenyl groups being equatorial; the anions are chloride
and O-nitrate respectively, the latter complex being
produced as a toluene solvate. A considerable variety
of related compounds has been structurally charac-
terized; those considered most relevant, comprising
The structural characterization of ‘Ph8Sb4O6’ resides
in the literature in two forms; one, recorded as
[(Ph8Sb4O6).(HOAc)3] dichloromethane solvate,11 is a
true tetranuclear basic acetate and, as such, not strictly
comparable with the ‘unsolvated’ bare parent. The
latter has been recorded in a triclinic cell; a 11ꢀ677(5),
ꢀ
b 9ꢀ745(3), c 10ꢀ586(6) A, ꢂ 99ꢀ69(4), ꢀ 113ꢀ35(3),
ꢀ
3
ꢀ
ꢃ 87ꢀ56(3) , V 1090 A , Z = 1 f.u.; the structure
was reꢂned to a residual of 0ꢀ051 for 2175 ‘observed’
(I > 3ꢁ(I)) reꢁections in terms of a model involving
a pair of essentially identical tetranuclear molecules
superimposed and centred about a common inversion
centre and disordered 50 : 50 in that manner.6 The

Short Communications
681
close similarity of a and b, 180 ꢁ ꢃ, and V of that
determination with the present b, c, ꢂ and V /2
suggested the present cell and reꢂnement in terms of
a non-disordered model comprising a pair of indepen-
dent centrosymmetric tetranuclear molecules, one-half
of each constituting the asymmetric unit, to be a
more appropriate description of an essentially similar
structure, notwithstanding the very acceptable residual
in the reꢂnement of the earlier disordered model. The
present resulting pair of molecules and their associated
very similar geometries are presented in Fig. 3 and
Tables 6 and 7, the most obvious non-trivial diꢃerences
being in respect of the disposition of the pendant phenyl
rings about the periphery. The novel array of the
Sb4O6 core comprises a pair of open cubes, each with
one corner missing with a common face containing
an inversion centre which relates them, the overall
symmetry being quasi-2/m.
A new crystalline (‘ꢀ’) phase of the parent triph-
enylstibine has been obtained from toluene/hexane
solution. As in the other (triclinic) phase,12 there
are two molecules in the asymmetric unit; these
are packed so as to confront each other, with lone
pairs everted, presumably in consequence of inter-
molecular interactions of a type recently described.13
Geometries are unexceptional with Sb–C ranging from
University of Auckland,14 recording the synthesis of
the above phase of (Ph3SbCl)2O (conꢂrmed by a unit
cell calibration) following the method recorded in ref. 7
for the bromide. He reports the presence of a (slightly
split) band at 765 cmꢂ1, attributed to Sb–O, similar
to that recorded for the product reported in ref. 15.
References
1
Bowmaker, G. A., Eꢂendy, Hart, R. D., Kildea, J. D.,
de Silva, E. N., Skelton, B. W., and White, A. H., Aust.
J. Chem., 1997, 50, 539.
Bowmaker, G. A., Hart, R. D., and White, A. H., Aust. J.
Chem., 1997, 50, 567.
Eꢂendy, Kildea, J. D., and White, A. H., Aust. J. Chem.,
1997, 50, 587.
Tiekink, E. R. T., J. Organomet. Chem., 1987, 333, 199.
2
3
4
5
Taylor, M. J., Baker, L.-J., Rickard, C. E. F., and Sur-
man, P. W. J., J. Organomet. Chem., 1995, 498, C14.
Bordner, J., Doak, G. O., and Everett, T. S., J. Am. Chem.
Soc., 1986, 108, 4206.
Ouchi, A., and Sato, S., Bull. Chem. Soc. Jpn, 1988, 61,
1806.
Ferguson, G., and Ridley, D. R., Acta Crystallogr., Sect.
B, 1973, 29, 2221.
6
7
8
9
Southerington, I. B., Forster, G. E., Begley, M. J., and
Sowerby, D. B., J. Chem. Soc., Dalton Trans., 1995, 1995.
Glidewell, C., J. Organomet. Chem., 1965, 356, 151.
Sowerby, D. B., Begley, M. J., and Millington, P. L.,
J. Chem. Soc., Chem. Commun., 1984, 896.
Adams, E. A., Kolis, J. W., and Pennington, W. T., Acta
Crystallogr., Sect. C, 1990, 46, 917.
Dance, I., and Scudder, M., Chem. Eur. J., 1996, 2, 481.
Taylor, M. J., and Rickard, C. E. F., unpublished data
(personal communication).
Doak, G. O., Long, G. G., and Freedman, L. D., J. Organomet.
Chem., 1965, 4, 82.
10
ꢀ
ꢀ
2ꢀ140(7) to 2ꢀ155(7) A (average 2ꢀ146 A) and tor-
sions C(mn1)–Sb(m)–C(mn+1 1)–C(mn+1 2) 93ꢀ3(6),
94ꢀ8(6), 79ꢀ9(6); 102ꢀ8(6), 95ꢀ8(6), 85ꢀ7(6)ꢀ, n = 1,
2, 3 respectively for molecules m = 1, 2.
11
12
13
14
Acknowledgment
15
We gratefully acknowledge correspondence with Pro-
fessor Michael J. Taylor of the Department of Chemistry,