Asymmetric diosmium sawhorse complexes

Article abstract of DOI:10.1107/S2053229619004236

Three asymmetric diosmium(I) carbonyl sawhorse complexes have been prepared by microwave heating. One of these complexes is of the type Os₂(μ-O₂CR)(μ-O₂CR^′ )(CO)₄L₂, with two different brid

Full text of DOI:10.1107/S2053229619004236

research papers
Asymmetric diosmium sawhorse complexes
a
a
a
a
Kylie M. Wilson, John W. Swartout, Henry A. Touchton, Erica N. Lambert,
ISSN 2053-2296
a
a
a
a
James E. Johnstone, Ashley K. Archambeau, David M. Marolf, Emily R. Mikeska,
b
c
d
Vincent M. Lynch, Vladimir N. Nesterov, Eric W. Reinheimer, Gregory L.
a
a
Powell * and Cynthia B. Powell
a
b
Chemistry & Biochemistry, Abilene Christian University, ACU Box 28132, Abilene, Texas 79699, USA, Chemistry,
Received 26 February 2019
Accepted 28 March 2019
c
University of Texas at Austin, 100 E. 24th St., Austin, Texas 78712, USA, Department of Chemistry, University of North
d
Texas, 1508 W. Mulberry St., Denton, TX 76201, USA, and Rigaku Americas, 9009 New Trails Dr., The Woodlands,
Texas 77381, USA. *Correspondence e-mail: powellg@acu.edu
Edited by G. P. A. Yap, University of Delaware,
USA
Three asymmetric diosmium(I) carbonyl sawhorse complexes have been
prepared by microwave heating. One of these complexes is of the type Os
Keywords: diosmium carbonyl cluster; asym-
metric sawhorse complex; mixed carboxylate
ligands; axial ligand substitution; crystal struc-
ture.
2
(ꢀ-
0
O CR)(ꢀ-O CR )(CO) L , with two different bridging carboxylate ligands,
2
2
4 2
while the other two complexes are of the type Os (ꢀ-O CR) (CO) L, with one
2
2
2
5
axial CO ligand and one axial phosphane ligand. The mixed carboxylate
complex Os (ꢀ-acetate)(ꢀ-propionate)(CO) [P(p-tolyl) ] , (1), was prepared by
2
4
3 2
CCDC references: 1869129; 1869128;
heating Os (CO) with a mixture of acetic and propionic acids, isolating Os (ꢀ-
1
869127; 1869126; 1869125; 1869124;
869305; 1869130
3
12
2
1
acetate)(ꢀ-propionate)(CO)
phosphane ligands. This is the first example of an Os sawhorse complex with
, and then replacing two CO ligands with two
6
2
Supporting information: this article has
two different carboxylate bridges. The syntheses of Os (ꢀ-acetate) (CO) [P(p-
2
2
5
supporting information at journals.iucr.org/c
tolyl) ], (3), and Os (ꢀ-propionate) (CO) [P(p-tolyl) ], (6), involved the
3
2
2
5
3
reaction of Os (CO) with the appropriate carboxylic acid to initially produce
3
12
Os (ꢀ-carboxylate) (CO) , followed by treatment with refluxing tetrahydro-
2
2
6
furan (THF) to form Os (ꢀ-carboxylate) (CO) (THF), and finally addition of
2
2
5
tri-p-tolylphosphane to replace the THF ligand with the P(p-tolyl) ligand.
3
Neutral complexes of the type Os (ꢀ-O CR) (CO) L had not previously been
2
2
2
5
subjected to X-ray crystallographic analysis. The more symmetrical disubstituted
complexes, i.e. Os (ꢀ-formate) (CO) [P(p-tolyl) ] , (8), Os (ꢀ-acetate) (CO) [P(p-
2
2
4
3 2
2
2
4
tolyl) ] , (4), and Os (ꢀ-propionate) (CO) [P(p-tolyl) ] , (7), as well as the
3
2
2
2
4
3 2
previously reported symmetrical unsubstituted complexes Os (ꢀ-acetate) -
2
2
(
CO) , (2), and Os (ꢀ-propionate) (CO) , (5), were also prepared in order to
6 2 2 6
examine the influence of axial ligand substitution on the Os—Os bond distance
in these sawhorse molecules. Eight crystal structures have been determined and
0
0
studied, namely ꢀ-acetato-1ꢁO:2ꢁO -ꢀ-propanoato-1ꢁO:2ꢁO -bis[tris(4-methyl-
0
phenyl)phosphane]-1ꢁP,2ꢁP -bis(dicarbonylosmium)(Os—Os) dichloromethane
monosolvate, [Os (C H O )(C H O )(C H P) (CO) ]ꢀCH Cl , (1), bis(ꢀ-
2
2
3
2
3
5
2
21 21
2
4
2
2
0
acetato-1ꢁO:2ꢁO )bis(tricarbonylosmium)(Os—Os), [Os (C H O ) (CO) ], (2)
(
2
2
3
2 2
6
0
2
3
redetermined structure), bis(ꢀ-acetato-1ꢁO:2ꢁO )pentacarbonyl-1ꢁ C,2ꢁ C-
[
tris(4-methylphenyl)phosphane-1ꢁP]diosmium(Os—Os), [Os (C H O ) (C H -
2
2
3
2 2 21 21
0
P)(CO) ], (3), bis(ꢀ-acetato-1ꢁO:2ꢁO )bis[tris(4-methylphenyl)phosphane]-1ꢁP,2ꢁP-
5
bis(dicarbonylosmium)(Os—Os) p-xylene sesquisolvate, [Os (C H O ) (C H P) -
2
2
2
3
2 2 21 21
0
(
[
CO) ]ꢀ1.5C H , (4), bis(ꢀ-propanoato-1ꢁO:2ꢁO )bis(tricarbonylosmium)(Os—Os),
0
2 3 5 2 2 6
4
8 10
2
3
Os (C H O ) (CO) ], (5), pentacarbonyl-1ꢁ C,2ꢁ C-bis(ꢀ-propanoato-1ꢁO:2ꢁO )-
[
(
tris(4-methylphenyl)phosphane-1ꢁP]diosmium(Os—Os), [Os (C H O ) (C H P)-
2
3
5 2 2 21 21
0
CO) ], (6), bis(ꢀ-propanoato-1ꢁO:2ꢁO )bis[tris(4-methylphenyl)phosphane]-
5
1
ꢁP,2ꢁP-bis(dicarbonylosmium)(Os—Os) dichloromethane monosolvate, [Os -
2
0
(C H O ) (C H P) (CO) ]ꢀCH Cl , (7), and bis(ꢀ-formato-1ꢁO:2ꢁO )bis-
3
5
2 2 21 21
2
4
2
2
[tris(4-methylphenyl)phosphane]-1ꢁP,2ꢁP-bis(dicarbonylosmium)(Os—Os), [Os -
2
(CHO ) (C H P) (CO) ], (8).
2 2 21 21 2 4
1
. Introduction
High-temperature reactions of Os (CO) with carboxylic
3 12
#
2019 International Union of Crystallography
acids produce diosmium(I) sawhorse complexes, Os (ꢀ-
2
Acta Cryst. (2019). C75
https://doi.org/10.1107/S2053229619004236 1 of 9

research papers
O CR) (CO) , with metal–metal single bonds (Crooks et al.,
2
2.2. Synthesis and crystallization
.2.1. Synthesis of (1). Os (CO) (100.5 mg, 0.111 mmol),
2
6
1969). As shown in Scheme 1, the Os—Os vector forms the top
2
3
12
of the sawhorse, while its legs consist of four equatorial CO
ligands (Bullitt & Cotton, 1971). Two cis-carboxylate ligands
are also bound in equatorial sites, and the remaining two CO
ligands are positioned along the metal–metal axis. Johnson,
Lewis, and co-workers first reported the preparation of these
complexes in 1969, and they demonstrated that both axial CO
ligands could be readily replaced by other ligands, including
pyridine or tertiary phosphanes (Crooks et al., 1969). In 1987,
Deeming and co-workers showed that it is possible to replace
only one of the axial CO ligands to produce asymmetric
compounds of the type Os (ꢀ-O CR) (CO) L (Deeming et al.,
acetic acid (2.5 ml), and propionic acid (3.0 ml) were placed in
a 35 ml glass reaction vessel and sealed with a polytetra-
fluoroethylene (PTFE)-lined cap. The mixture was stirred and
ꢂ
irradiated in a CEM Discover-SP microwave reactor at 180 C
for 10 min. The excess acids were evaporated under a stream
2
2
2
5
1
987). They refluxed a solution of Os (ꢀ-O CR) (CO) in
2 2 2 6
tetrahydrofuran (THF) to form Os (ꢀ-O CR) (CO) (THF),
2
2
2
5
and then replaced the THF ligand with a phosphane ligand
L). No crystal structures of neutral asymmetric Os sawhorse
complexes have been reported, but one anionic complex,
(
2
ꢁ
[
Os (ꢀ-O CCH ) Cl(CO) ] , containing one chloride ligand
2
2
3 2
5
and one CO ligand in the axial positions, has been isolated and
subjected to X-ray crystallographic analysis (Deeming et al.,
of compressed air, and the residue was redissolved in di-
chloromethane. TLC with an eluent of 7:3:1 heptane–di-
chloromethane–toluene gave four colorless bands, which were
1987).
The use of microwave heating to prepare diosmium(I)
sawhorses was first described in 2013 (Pyper et al., 2013). A
few new complexes were prepared and structurally char-
acterized, and it was noted that metal–metal bond distances
seemed to be correlated with the strength of the parent
carboxylic acid. With increasing acid strength, the Os—Os
bond distances get slightly longer. Since then, the microwave-
assisted syntheses of several additional sawhorse complexes
containing mono- and dicarboxylate ligands have been
reported (Fikes et al., 2014; Chor et al., 2016; Gwini et al.,
collected under UV light. Band 1 (R = 0.87) consisted of
F
1
2
0
0.9 mg (11.9% yield) of Os (ꢀ-H) (CO) . IR (ꢂCO, CHCl3):
4 4 12
ꢁ
1
085 (m), 2067 (vs), 2020 (s), 1997 (w) cm . Band 2 (R =
F
.79) consisted of 29.4 mg (26.6% yield) of Os (ꢀ-acet-
2
ate) (CO) . IR (ꢂ , CHCl ): 2100 (m), 2067 (vs), 2015 (s),
2
6
CO
3
ꢁ
998 (vs) cm . Band 3 (R = 0.74) consisted of 38.7 mg
F
1
1
(
34.2% yield) of Os (ꢀ-acetate)(ꢀ-propionate)(CO) . IR
2 6
ꢁ1
(
Band 4 (R = 0.67) consisted of 22.9 mg (19.9% yield) of
ꢂCO, CHCl ): 2100 (m), 2066 (vs), 2014 (s), 1997 (vs) cm .
3
F
2017). The goals of the current project were twofold: (i) to
synthesize a sawhorse complex of the type Os (ꢀ-O CR)(ꢀ-
2
2
0
O CR )(CO) with two different bridging carboxylate ligands,
6
2
and (ii) to perform single-crystal diffraction studies of at least
one series of complexes with the formulae Os (ꢀ-O CR) -
2
2
2
(
CO) , Os (ꢀ-O CR) (CO) L, and Os (ꢀ-O CR) (CO) L , in
6 2 2 2 5 2 2 2 4 2
order to investigate the trend in Os—Os bond lengths. We now
report that these goals have been met.
2
. Experimental
2.1. Materials and methods
Os (CO) and tri-p-tolylphosphane were purchased from
12
3
Strem, while the other reagents were purchased from Sigma–
Aldrich. All chemicals were used as received, and all opera-
tions were performed without taking precautions to exclude
air and moisture. Os (ꢀ-acetate) (CO) , (2), Os (ꢀ-propio-
2
2
6
2
nate) (CO) , (5), and Os (ꢀ-formate) (CO) , (10), were pre-
2
6
2
2
6
pared according to published procedures (Pyper et al., 2013).
IR spectra were acquired using a Nicolet Avatar 320 FT–IR
1
spectrometer with a CaF solution cell. H NMR spectra were
2
recorded at 60 MHz on an Anasazi Eft-60 spectrometer.
Preparative thin-layer chromatography (TLC) was carried out
on Analtech silica gel 60 (0.50 mm) plates. Atlantic Microlab
performed the elemental analyses.
Os (ꢀ-propionate) (CO) . IR (ꢂ , CHCl ): 2100 (m), 2066
2
2
6
CO
3
ꢁ
1
(vs), 2014 (s), 1997 (vs) cm . The residue from band 3 was
dissolved in 1,2-dichloroethane (25 ml) and acetonitrile
ꢃ
2
of 9 Wilson et al. Asymmetric diosmium sawhorse complexes
Acta Cryst. (2019). C75

research papers
Table 1
Experimental details.
H-atom parameters were constrained.
(1)
(2)
(3)
(4)
Crystal data
Chemical formula
[Os (C
2
H
2 3
2
O )(C
3 5 2
H O )-
[Os
2
(C H
2 3
O )
2 2
(CO)
6
]
[Os (C
2
2
H O )
3 2 2
(C21
H21P)-
2 2 3 2 2 2
[Os (C H O ) (C21H21P) -
(
CH
C
21
H
Cl
2 2
21P)
2
(CO)
4
]ꢀ-
5
(CO) ]
(CO)
4
8 10
]ꢀ1.5C H
M
r
1318.17
Monoclinic, P2
100
666.55
Monoclinic, P2
200
7.6949 (5), 14.3612 (10),
13.8623 (9)
90, 105.202 (1), 90
942.88
Triclinic, P1
100
10.452 (4), 11.229 (4),
13.045 (5)
82.813 (6), 89.157 (8),
1378.46
Triclinic, P1
293
12.81225 (16), 14.8455 (2),
16.6818 (2)
98.1785 (11), 101.7904 (11),
Crystal system, space group
Temperature (K)
˚
a, b, c (A)
1
/c
1
/n
18.5007 (4), 18.5396 (4),
4.8090 (3)
90, 91.9976 (17), 90
1
ꢂ
ꢃ, ꢄ, ꢅ ( )
89.457 (9)
1518.8 (10)
2
Mo Kꢃ
8.46
0.27 ꢄ 0.14 ꢄ 0.12
113.3846 (14)
2761.37 (7)
2
Cu Kꢃ
9.55
0.11 ꢄ 0.07 ꢄ 0.02
˚
3
V (A )
Z
Radiation type
ꢀ (mm
Crystal size (mm)
5076.35 (18)
4
Cu Kꢃ
11.30
1478.29 (17)
4
Mo Kꢃ
17.22
ꢁ
1
)
0.22 ꢄ 0.06 ꢄ 0.03
0.19 ꢄ 0.12 ꢄ 0.07
Data collection
Diffractometer
Rigaku SuperNova AtlasS2
CCD
Bruker APEXII CCD
Rigaku SCX-Mini Mercury
2+ CCD
Rigaku SuperNova
AtlasS2 CCD
Absorption correction
Gaussian (CrysAlis PRO;
Rigaku OD, 2017)
0.428, 1.000
Multi-scan (SADABS;
Bruker, 2008)
0.295, 0.747
Multi-scan (ABSCOR;
Higashi, 2001)
0.605, 1.00
Gaussian (CrysAlis PRO;
Rigaku OD, 2017)
0.626, 1.000
Tmin, Tmax
No. of measured, indepen-
dent and observed [I >
20129, 9265, 8475
14002, 3252, 3003
32350, 6915, 6534
49090, 9768, 8691
2
ꢆ(I)] reflections
R
int
0.024
0.602
0.046
0.641
0.032
0.648
0.066
0.595
˚
ꢁ1
)
(sin ꢇ/ꢈ)max (A
Refinement
2
2
2
R[F > 2ꢆ(F )], wR(F ), S
No. of reflections
0.023, 0.055, 1.00
9265
0.023, 0.055, 1.09
3252
0.020, 0.045, 1.02
6915
0.027, 0.068, 1.05
9768
No. of parameters
No. of restraints
Áꢉmax, Áꢉmin (e A
632
112
1.16, ꢁ1.05
202
0
1.80, ꢁ1.33
385
0
2.80, ꢁ1.05
678
0
2.09, ꢁ1.11
˚
ꢁ3
)
(5)
(6)
(7)
(8)
Crystal data
Chemical formula
[Os (C
2
3
H
5
O
2
)
2
(CO)
6
]
[Os
CO)
970.94
Triclinic, P1
100
10.0952 (2), 11.6630 (3),
13.7536 (3)
88.6185 (19), 86.7627 (18),
2
(C
3
H
5
O
2
)
2
(C21
H
21P)-
[Os (C
2
(CO)
3
H
5
O
2
)
2
(C21
Cl
H
2
21P) -
2 2 2 2
[Os (CHO ) (C21H21P) -
(CO) ]
4
(
5
]
4
]ꢀCH
2
2
M
r
694.60
Orthorhombic, Pbca
100
1332.20
Monoclinic, P2
100
18.4968 (6), 18.7369 (7),
14.9214 (6)
90, 91.806 (2), 90
1191.17
Triclinic, P1
200
10.7707 (4), 10.8014 (4),
20.3790 (7)
104.393 (1), 91.009 (1),
98.993 (1)
2264.27 (14)
2
Crystal system, space group
Temperature (K)
˚
a, b, c (A)
1
/c
9.79942 (10), 15.51827 (19),
1.7339 (2)
90, 90, 90
2
ꢂ
ꢃ, ꢄ, ꢅ ( )
86.9563 (19)
˚
3
V (A )
3305.08 (6)
8
Cu Kꢃ
29.08
1614.12 (6)
2
Cu Kꢃ
15.55
5168.8 (3)
4
Mo Kꢃ
5.13
Z
Radiation type
Mo Kꢃ
5.73
0.15 ꢄ 0.11 ꢄ 0.04
ꢁ
1
ꢀ
(mm
Crystal size (mm)
)
0.08 ꢄ 0.06 ꢄ 0.04
0.21 ꢄ 0.14 ꢄ 0.06
0.28 ꢄ 0.12 ꢄ 0.09
Data collection
Diffractometer
Rigaku SuperNova AtlasS2
CCD
Multi-scan CrysAlis PRO
Rigaku SuperNova AtlasS2
CCD
Multi-scan CrysAlis PRO
(Rigaku OD, 2015)
0.389, 1.000
Rigaku SCX-Mini Mercury
2+ CCD
Multi-scan (ABSCOR;
Higashi, 2001)
0.673, 1.00
Bruker APEXII CCD
Absorption correction
Multi-scan (SADABS;
Bruker, 2008)
0.538, 0.746
(Rigaku OD, 2015)
Tmin, Tmax
0.637, 1.000
16571, 3300, 3196
No. of measured, indepen-
dent and observed [I >
30757, 6461, 6196
54214, 11794, 9639
30910, 9960, 8554
2
ꢆ(I)] reflections
R
int
0.027
0.622
0.038
0.622
0.060
0.649
0.058
0.641
˚
ꢁ1
)
(sin ꢇ/ꢈ)max (A
Refinement
2
2
2
R[F > 2ꢆ(F )], wR(F ), S
No. of reflections
0.018, 0.039, 1.03
3300
0.019, 0.046, 1.08
6461
0.036, 0.071, 1.07
11794
0.030, 0.082, 1.06
9960
ꢃ
Acta Cryst. (2019). C75
Wilson et al.
Asymmetric diosmium sawhorse complexes 3 of 9

research papers
Table 1 (continued)
(5)
(6)
(7)
(8)
No. of parameters
No. of restraints
Áꢉmax, Áꢉmin (e A
219
0
0.55, ꢁ0.93
402
0
0.55, ꢁ1.21
624
20
1.39, ꢁ1.32
548
0
1.19, ꢁ1.09
˚
ꢁ3
)
Computer programs: CrysAlis PRO (Rigaku OD, 2015, 2017), APEX2 (Bruker, 2009), CrystalClear (Rigaku, 2008), SAINT (Bruker, 2009), SHELXT (Sheldrick, 2015a), SIR97
(Altomare et al., 1999), SHELXL2018 (Sheldrick, 2015b), SHELXL2013 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009), and XP in SHELXTL/PC (Sheldrick, 1990).
(5 ml). Tri-p-tolylphosphane (0.0260 g, 0.0854 mmol) was
The first and second bands contained 2.7 mg of Os (ꢀ-H) -
4 4
added and the mixture was refluxed for 50 min. The solvent
was removed and the residue was dissolved in CH Cl . TLC
with an eluent of 3:2 hexanes–dichloromethane gave two
(CO)12 and 7.1 mg of (2), respectively. Band 3 consisted of
54.0 mg (54.1% yield) of (4). IR (ꢂ , CHCl ): 2011 (vs), 1967
2
2
CO
3
ꢁ
1 1
(w), 1934 (vs) cm . H NMR (CDCl ): ꢊ 7.35 (m, 24H), 2.36
3
major bands. Band 1 consisted of 9.7 mg of unreacted Os (ꢀ-
(m, 18H), 1.60 (t, 6H). Analysis calculated (%) for C50H48-
O Os P : C 49.25, H 3.97; found: C 50.02, H 4.08. Single
2
acetate)(ꢀ-propionate)(CO) . Band 2 consisted of 36.8 mg of
6
8
2 2
(
(
1) [18.0% yield based on Os (CO) ]. IR (ꢂ , CHCl ): 2011
crystals were obtained by slow evaporation of a p-xylene
solution at ambient temperature.
3
12
CO
3
ꢁ1 1
vs), 1967 (m), 1934 (vs) cm . H NMR (CDCl ): ꢊ 7.30 (m,
3
24H), 2.35 (s, 18H), 1.88 (q, 2H), 1.59 (s, 3H), 0.58 (t, 3H).
Analysis calculated (%) for C H O Os P : C 49.67, H 4.09;
2.2.4. Synthesis of (6). The procedure described above for
the synthesis of (3) was employed. Os (CO) (80.6 mg,
51
50
8
2
2
3
12
found: C 49.78, H 4.04. Single crystals suitable for X-ray
diffraction were obtained by slow diffusion of n-hexane into a
dichloromethane solution at ambient temperature.
0.0889 mmol), propionic acid (6.5 ml), and tri-p-tolyl-
phosphane (39.3 mg, 0.129 mmol) were used. TLC with an
eluent of 1:1 hexanes–CH Cl produced three bands. Band 1
2
2
2.2.2. Synthesis of (3). A mixture of Os (CO) (80.2 mg,
.0884 mmol) and acetic acid (6 ml) was stirred and irradiated
in a microwave reactor at 180 C for 10 min. The excess acid
was evaporated under a stream of air and the residue was
redissolved in tetrahydrofuran (25 ml). This solution was
consisted of 13.1 mg (17.8% yield) of Os (ꢀ-H) (CO) . Band
4 4 12
2 consisted of 3.6 mg (2.2% yield) of Os (ꢀ-propionate) -
2 2
(CO) [P(p-tolyl) ] , (7). Band 3 consisted of 57.8 mg (44.6%
4 3 2
3
12
0
ꢂ
yield) of Os (ꢀ-propionate) (CO) [P(p-tolyl) ], (6). IR (ꢂ ,
CO
2
2
5
3
ꢁ
1 1
CHCl ): 2072 (vs), 2002 (vs), 1976 (s), 1923 (m) cm . H NMR
3
refluxed for 2.5 h with vigorous stirring and then cooled to
ꢂ
(CDCl ): ꢊ 7.40 (m, 12H), 2.39 (m, 9H), 2.05 (q, 4H), 0.86 (t,
3
0
C in an ice bath. A second solution consisting of tri-p-
6H). Analysis calculated (%) for C H O Os P: C 39.58, H
31
32
9
2
tolylphosphane (30.4 mg, 0.0999 mmol) dissolved in THF
20 ml) was added dropwise over a period of 1 h to the solu-
3.22; found: C 39.97, H 3.36. Single crystals were obtained by
slow diffusion of n-hexane into a dichloromethane solution at
ambient temperature.
(
tion in the ice bath. The resulting mixture was allowed to
warm slowly to room temperature and the solvent was then
removed by rotary evaporation. The residue was dissolved in
CH Cl and subjected to TLC with an eluent of 1:1 hexanes–
2.2.5. Synthesis of (7). The procedure described above for
the synthesis of (4) was employed. Os (CO) (78.4 mg,
3
12
0.0865 mmol), propionic acid (8 ml), and tri-p-tolylphosphane
(123.7 mg, 0.406 mmol) were used. Two TLC bands were
collected. Band 1 consisted of 7.4 mg of Os (ꢀ-H) (CO) .
2
2
CH Cl . Four bands were collected. Band 1 (R = 0.90)
2
2
F
consisted of 3.7 mg (5.1% yield) of Os (ꢀ-H) (CO) . Band 2
4
4
12
4
4
12
(
acetate) (CO) , (2). Band 3 (R = 0.43) consisted of 10.8 mg
R = 0.54) consisted of 14.2 mg (16.1% yield) of Os (ꢀ-
Band 2 consisted of 89.9 mg (55.5% yield) of Os (ꢀ-propio-
F
2
2
nate) (CO) [P(p-tolyl) ] , (7). IR (ꢂ , CHCl ): 2011 (vs),
2
6
F
2
4
3 2
CO
3
ꢁ
1 1
(
(
(
6.7% yield) of Os (ꢀ-acetate) (CO) [P(p-tolyl) ] , (4). IR
1967 (w), 1934 (vs) cm . H NMR (CDCl ): ꢊ 7.36 (m, 24H),
2
2
4
3 2
3
ꢁ
1
ꢂCO, CHCl ): 2011 (vs), 1967 (m), 1935 (vs) cm . Band 4
2.36 (m, 18H), 1.83 (q, 4H), 0.59 (t, 6H). Analysis calculated
(%) for C H O Os P : C 50.07, H 4.20; found: C 50.02, H
3
R = 0.35) consisted of 34.3 mg (27.4% yield) of Os (ꢀ-
F
2
52 52
8
2 2
acetate) (CO) [P(p-tolyl) ], (3). IR (ꢂ , CHCl ): 2072 (vs),
4.18. Single crystals were obtained by slow diffusion of
n-hexane into a dichloromethane solution at ambient tem-
perature.
2
5
3
CO
3
ꢁ
1 1
2
001 (vs), 1977 (s), 1923 (m) cm . H NMR (CDCl ): ꢊ 7.39
3
(
for C H O Os P: C 38.21, H 2.89; found: C 38.57, H 2.99.
m, 12H), 2.40 (m, 9H), 1.54 (s, 6H). Analysis calculated (%)
2.2.6. Synthesis of (8). Os (ꢀ-formate) (CO) (59.6 mg,
3
0
27
9
2
2
2
6
Single crystals were obtained by slow diffusion of n-hexane
into a dichloromethane solution at ambient temperature.
0.0933 mmol) and tri-p-tolylphosphane (142 mg, 0.467 mmol)
were dissolved in a mixture of chloroform (25 ml) and
acetonitrile (3 ml). The solution was refluxed for 1 h. The
solvent was removed and the residue was dissolved in CH Cl .
2.2.3. Synthesis of (4). A mixture of Os (CO) (49.4 mg,
.0545 mmol) and acetic acid (7 ml) was stirred and irradiated
in a microwave reactor at 185 C for 10 min. The excess acid
was evaporated under a stream of air and the residue was
redissolved in a mixture of chloroform (25 ml) and acetonitrile
3 12
0
2
2
ꢂ
TLC with an eluent of 1:1 hexanes–CH Cl produced one
2 2
major band, which consisted of 73.8 mg (66.4% yield) of
Os (ꢀ-formate) (CO) [P(p-tolyl) ] , (8). IR (ꢂCO, CHCl3):
2
2
4
3 2
ꢁ
1
2012 (vs), 1969 (w), 1938 (vs) cm . Analysis calculated (%)
(3 ml). Tri-p-tolylphosphane (81.7 mg, 0.268 mmol) was added
and the solution refluxed for 55 min. The solvent was removed
and the residue dissolved in CH Cl . Three bands were
collected after TLC with an eluent of 1.25:1 hexanes–CH Cl .
for C H O Os P : C 48.40, H 3.72; found: C 47.36, H 3.65%.
2 2
48
44
8
Single crystals were obtained by slow evaporation of a con-
centrated dichloromethane solution at ambient temperature.
2
2
2
2
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2.2.7. Crystallization of (5). Single crystals of (2) were
obtained by slow diffusion of n-hexane into a dichloro-
methane solution at ambient temperature. Single crystals of
(5) were obtained by slow diffusion of n-pentane into a
chloroform solution at ambient temperature.
2.3. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. All H atoms were placed in
calculated positions and refined using a riding model. For (1),
both bridging carboxylate positions encompassed acetate and
propionate moieties disordered in 50:50 ratios with respect to
one another. Bond distances between the carboxylate C atoms
and the methyl and ethyl groups were restrained to idealized
values, and the anisotropic displacement parameters of the
acetate and propionate C and O atoms were restrained. For
(7), the methyl group of one propionate ligand is disordered so
that there are two alternative orientations for that terminal C
Figure 2
atom (C45 and C45A). The occupancy ratio refined to
0.726 (13):0.274 (13). The geometry of the two components
was restrained to be equivalent, atoms C45 and C45A were
restrained to approximate isotropic behavior, and similar
anisotropic displacement parameters were used for both
atoms.
The structure of the core portion of complex (1), showing the 50:50
disorder of the bridging acetate and propionate ligands. The phosphane
ligands have been omitted for clarity.
convert the asymmetric product Os (ꢀ-acetate)(ꢀ-propion-
2
ate)(CO) into Os (ꢀ-acetate)(ꢀ-propionate)(CO) [P(p-tol-
6
2
4
yl) ] , (1), before conducting further studies. As expected, the
3
2
3
. Results and discussion
overall yield was low at 18%. Two three-membered series of
Os (ꢀ-O CR) (CO) L complexes, in which L is tri-p-tolyl-
3.1. Synthesis and spectroscopy
2
2
2
6–n n
phosphane and n = 0, 1, or 2, were prepared by similar
methods. One such series consists of complexes (2), (3), and
A combination of Os (CO) , acetic acid, and propionic
12
3
acid was used to successfully synthesize the first example of a
mixed carboxylate sawhorse complex, namely Os (ꢀ-acetate)-
(
4), for which R = Me (acetate) and n = 0, 1, and 2, respec-
2
tively. The other series consists of complexes (5), (6), and (7),
for which R = Et (propionate) and n = 0, 1, and 2, respectively.
The yields for complexes (2), (5), and (10) with no phosphane
ligands (n = 0) were 90% or greater (Pyper et al., 2013). The
yields for the three disubstituted complexes (4), (7), and (8),
with n = 2, were between 54 and 66%. The yields for the two
(
ꢀ-propionate)(CO) , which was sandwiched between Os (ꢀ-
6 2
acetate) (CO)6 and Os (ꢀ-propionate) (CO) on the pre-
2
2
2
6
parative TLC plates. We have observed that the latter two
compounds decompose slowly over a period of several weeks.
However, upon replacing the two axial CO ligands in these
compounds with phosphane ligands, the resulting complexes
are stable for months or years. Thus, we chose to immediately
Figure 1
The molecular structure of the metal complex in (1). H atoms and solvent
molecules have been omitted for clarity. Displacement ellipsoids are
drawn at the 50% probability level.
Figure 3
The molecular structure of (2), with displacement ellipsoids drawn at the
50% probability level.
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Asymmetric diosmium sawhorse complexes 5 of 9

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Table 2
Carbonyl stretching frequencies of the diosmium sawhorse complexes
2 2 2 n
(1)–(10) of the type Os (O CR) (CO)6–nL for which n = 0, 1, or 2, and L
is tri-p-tolylphosphane.
ꢁ
1
Complex
ꢂCO (cm )
Os
Os
Os
Os
Os
Os
Os
Os
Os
Os
2
2
2
2
2
2
2
2
2
2
(acetate)
(propionate)
(benzoate)
(formate) (CO)
(acetate) (CO)
(propionate) (CO)
(acetate)(propionate)(CO)
2
(CO)
6
, (2)
2100 (m), 2067 (vs),
015 (s), 1998 (vs)
2099 (m), 2066 (vs),
014 (s), 1997 (vs)
2099 (m), 2066 (vs),
015 (s), 1998 (vs)
2104 (m), 2071 (vs),
021 (s), 2004 (vs)
2072 (vs), 2001 (vs),
977 (s), 1923 (m)
2072 (vs), 2002 (vs),
976 (s), 1923 (m)
2011 (vs), 1967 (m),
934 (vs)
2011 (vs), 1967 (m),
934 (vs)
2011 (vs), 1967 (m),
934 (vs)
2017 (vs), 1972 (m),
941 (vs)
2
2
6
(CO) , (5)
2
2
(CO)
, (10)
[P(p-tolyl)
[P(p-tolyl)
[P(p-tolyl)
, (4)
[P(p-tolyl) , (7)
, (8)
6
, (9)
2
2
6
2
2
5
3
], (3)
1
2
5
3
], (6)
1
Figure 5
The molecular structure of (4), with displacement ellipsoids drawn at the
50% probability level. H atoms and solvent molecules have been omitted
for clarity.
4
3 2
] , (1)
1
(acetate)
(propionate)
(formate)
2
(CO)
4
[P(p-tolyl)
3
]
2
1
2
(CO)
4
3 2
]
1
2 4 3 2
(CO) [P(p-tolyl) ]
three absorption maxima with a vs/m/vs pattern. The ꢂCO
frequencies for the formate complexes are higher than those
containing the other carboxylate ligands. This is most likely
due to the fact that formate is the weakest base among these
ligands, which results in a lesser amount of Os—CO ꢋ-back-
bonding and comparatively stronger C—O bonds in the
formate complexes.
1
asymmetric complexes (3) and (6), with n = 1, were clearly the
lowest at 27 and 45%, respectively.
All of the complexes display characteristic IR carbonyl
ꢁ
1
stretching frequencies in the range 1900–2110 cm . The ꢂ
CO
frequencies of complexes (1)–(10) are reported in Table 2. The
degree of phosphane substitution is easily determined by
examination of the IR spectra. Complexes with no phosphane
ligands (n = 0) display four absorption maxima with an m/vs/s/
vs pattern. Complexes with one phosphane ligand (n = 1) show
four absorption maxima, but the pattern is vs/vs/s/m.
Complexes with two phosphane ligands (n = 2) display only
3.2. X-ray crystallography
X-ray data were collected at 100 K for five of the new
complexes [i.e. (1), (3), (5), (6), and (7)], at 200 K for two [i.e.
(
2) and (8)], and at 293 K for complex (4). The data collection
temperature for previously reported complexes (9) and (10)
was 100 K. Using the same temperature for all of the
diffraction experiments would have been ideal for the
purposes of comparing the structural details, however, the
bond lengths and angles associated with the Os atoms at the
Figure 4
The molecular structure of (3), with displacement ellipsoids drawn at the
Figure 6
The molecular structure of (5), with displacement ellipsoids drawn at the
50% probability level.
50% probability level.
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Table 3
Os—Os bond lengths (A) for eight Os
complexes (L is tri-p-tolylphosphane).
˚
2
(O
2
CR)
2
(CO)6–n
L
n
sawhorse
Carboxylate group
n = 0
n = 1
n = 2
Formate
Acetate
Propionate
2.7545 (2)
2.7419 (3)
2.7523 (2)
–
2.7388 (2)
2.7534 (2)
2.7677 (3)
2.7624 (8)
2.7479 (2)
core of these complexes are unlikely to vary significantly over
this temperature range.
The complexes reported herein all have the typical
sawhorse molecular geometry, with two cis-carboxylate
ligands, four equatorial CO ligands, two axial CO or phos-
phane ligands, and a metal–metal single bond. The molecular
structure of the metal complex in (1) is illustrated in Fig. 1. Not
surprisingly, there is disorder associated with the methyl group
of the acetate ligand and the ethyl group of the propionate
ligand such that each appears at both carboxylate positions
Figure 8
The molecular structure of (7), with displacement ellipsoids drawn at the
0% probability level. Tolyl H atoms and solvent molecules have been
5
omitted for clarity.
bond distance for the acetate series [complexes (2) and (3)],
but a decrease in the Os—Os distance for the propionate
series [complexes (5) and (6)]. Replacing a second axial CO
ligand with another phosphane ligand resulted in a decrease in
the Os—Os bond distance for the acetate series [(3) and (4)],
but an increase in the Os—Os distance for the propionate
series [(6) and (7)]. There was an overall increase in the
Os—Os distance in both the acetate and propionate
complexes when two CO ligands were replaced by two phos-
phane ligands, but this distance decreased in the formate
complexes. No logical pattern could be deduced.
50% of the time. The disordered ligands are shown in Fig. 2.
The molecular geometries of (2), (3), and (4) are illustrated in
Figs. 3, 4, and 5, respectively. A crystal structure of (2) was
reported in 1971 (Bullitt & Cotton, 1971), but we chose to
repeat this analysis in order to obtain more precise structural
details. The molecular structures of (5), (6), and (7) are illu-
strated in Figs. 6, 7, and 8, respectively. The complexes Os (ꢀ-
2
formate) (CO) , (10), and Os (ꢀ-formate) (CO) [P(p-tolyl) ] ,
2
6
2
2
4
3 2
(
(
8), were also included in this study. The crystal structure of
10) was reported several years ago (Pyper et al., 2013). The
molecular structure of (8) is illustrated in Fig. 9.
As mentioned above, it was suggested previously that the
Os—Os bond distances in diosmium(I) carbonyl sawhorse
complexes are correlated with the strength of the parent
carboxylic acid (Pyper et al., 2013). Metal–metal distances
became slightly longer as the acid strength increased (or as the
strength of the conjugate base decreased). At that time,
however, only three such sawhorse complexes had been
We assumed that the Os—Os bond distances in each series
would steadily change with an increasing number of phos-
phane ligands. Clearly, that was not the case. The Os—Os
bond distances for (2)–(8) and Os (ꢀ-formate) (CO) are
2
2
6
˚
listed in Table 3. The values range from 2.7388 (2) A for (8) to
˚
.7677 (3) A for (7). Replacing one axial carbonyl ligand with
2
one phosphane ligand resulted in an increase in the Os—Os
subjected to X-ray crystallographic analysis, namely Os (ꢀ-
2
acetate) (CO) , (2), Os (ꢀ-benzoate) (CO) , (9), and Os (ꢀ-
2
6
2
2
6
2
formate) (CO) , (10). In addition, the 1971 crystal structure of
6
2
Figure 7
The molecular structure of (6), with displacement ellipsoids drawn at the
Figure 9
The molecular structure of (8), with displacement ellipsoids drawn at the
50% probability level. All tolyl H atoms have been omitted for clarity.
50% probability level. All tolyl H atoms have been omitted for clarity.
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Asymmetric diosmium sawhorse complexes 7 of 9

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Table 4
Os—Os bond lengths (A) and parent acid pK
Os (O CR) (CO) complexes.
Table 5
Os—Os bond lengths (A) and average Ceq—Os—Os—Ceq torsion angles
˚
˚
a
values for four
Os—Os
ꢂ
2
2
2
6
( ) for 11 Os
tolylphosphane).
2
(O
2
CR)
2
(CO)6–n
L
n
sawhorse molecules (L is tri-p-
Compound
Acid pK
a
Average
torsion
angle
Os
Os
Os
Os
Os
2
2
2
2
2
(formate) (CO)
2
6
, (10)
3.75
4.19
4.19
4.76
4.88
2.7545 (2)
2.7495 (3)
2.7470 (3)
2.7419 (3)
2.7523 (2)
Bond
length
(benzoate)
(benzoate)
2
(CO)
(CO)
6
, (9A)
, (9B)
Compound
2
6
(acetate)
2
(CO)
6
, (2)
, (5)
Without phosphane ligands
(propionate)
2
(CO)
6
Os
Os
Os
Os
Os
2
2
2
2
2
(acetate) (CO)
2
6
, (2)
, (5)
2.7419 (3)
2.7523 (2)
2.7495 (3)
2.7470 (3)
2.7545 (2)
9.2 (8)
4.0 (5)
1.2 (9)
10.8 (6)
2.9 (3)
(propionate)
(benzoate)
(benzoate)
2
(CO)
6
2
(CO)
(CO)
6
, (9A)
, (9B)
2
6
the acetate complex was somewhat rudimentary by present
day standards. After obtaining the crystal structure of Os (ꢀ-
2 6
(formate) (CO) , (10)
2
propionate) (CO) and redetermining the structure of Os (ꢀ-
With phosphane ligands
2
6
2
acetate) (CO) , we can now report that there is no apparent
2
Os
Os
Os
Os
Os
Os
2
2
2
2
2
2
(acetate)(propionate)(CO)
4
[P(p-tolyl)
], (3)
, (4)
3
]
2
, (1)
2.7623 (2)
2.7624 (8)
2.7534 (2)
2.7479 (2)
2.7677 (3)
2.7388 (2)
6.3 (6)
9.2 (9)
13 (3)
19.1 (3)
6.8 (4)
21.7 (5)
6
(acetate)
(acetate)
2
(CO)
(CO)
5
[P(p-tolyl)
[P(p-tolyl)
3
correlation between the Os—Os bond distance and the basi-
city of the carboxylate ligands. Table 4 lists the Os—Os bond
2
4
3
]
2
(propionate)
(propionate)
2
(CO)
(CO)
5
[P(p-tolyl)
[P(p-tolyl)
3
], (6)
, (7)
distance along with the parent acid pKa for the Os (ꢀ-
2
4
3
]
2
2
2 4 3 2
(formate) (CO) [P(p-tolyl) ] , (8)
O CR) (CO) complexes, in which R is H, Me, Et, and Ph. The
6
2
2
two complexes containing the carboxylate groups with the
highest and lowest basicity, i.e. propionate and formate,
respectively, have the two longest Os—Os bonds, while the
acetate complex (with the second highest carboxylate basicity)
has the shortest Os—Os bond. Neither the basicity of the
carboxylate ligands nor the number of phosphane ligands have
a predictable influence on the metal–metal bond length.
There are two independent molecules per unit cell in the
assumed that crystal packing forces are primarily responsible
for the torsional twists in these complexes, and we thought the
presence of relatively bulky phosphane ligands would have a
significantly different effect on the arrangement of molecules
in the crystal lattice versus the absence of such ligands. Thus,
we divided the complexes into two categories: (i) those con-
taining one or two axial phosphane ligands and (ii) those with
only CO ligands in axial positions. The data are listed in
Table 5. A plot of average C —Os—Os—C torsion angle
versus Os—Os bond length with two different trend lines, one
for the five molecules with no phosphane ligands and another
for the six molecules with phosphane ligands, is given in Fig. 10.
For both series, there is a steady decrease in the Os—Os bond
length as the average torsion angle increases. The slopes of the
two trend lines differ by less than 5%.
previously reported crystal structure of Os (ꢀ-benzoate) -
2
2
(
(
CO) , (9) (Pyper et al., 2013). One of these molecules, i.e
6
˚
9A), has an Os—Os bond distance of 2.7495 (3) A, while the
eq
eq
˚
other, i.e (9B), has an Os—Os bond distance of 2.7470 (3) A.
These molecules also have significantly different average
C —Os—Os—C (where Ceq is an equatorial carbonyl C
eq
eq
atom) torsion angles. The longer Os—Os bond length is
associated with the molecule that has the smaller torsion
angle. We wondered whether this might be a general trend, so
we plotted Os—Os bond distance versus the average C —
eq
Os—Os—Ceq torsion angle for the complexes in this study. We
4
. Conclusions
Three new asymmetric diosmium(I) carbonyl sawhorse com-
plexes were prepared and structurally characterized, including
the first sawhorse complex that contains two different
carboxylate ligands and the first two sawhorse complexes
containing only one tri-p-tolylphosphane ligand. A total of
eight crystal structures of Os sawhorse complexes have been
2
reported herein, and the Os—Os bond distances in these
˚
complexes range from 2.7419 (3) to 2.7677 (3) A. Several
factors may influence the length of the Os—Os single bonds,
but it appears as if torsional twisting around the Os—Os axis
has a more significant effect than the basicity of the
carboxylate ligands or the number of axial phosphane ligands.
In general, as the average C —Os—Os—C torsion angle
eq
eq
Figure 10
Plots of average Ceq—Os—Os—Ceq torsion angle versus Os—Os bond
increases, the Os—Os bond distance decreases. More struc-
tural data involving additional sawhorse complexes is needed
to confirm this trend, but it is noteworthy that the complex
2 2 2 6
distance for (A) five Os (O CR) (CO) sawhorse molecules and (B) six
Os (O CR) sawhorse molecules. Data points are numbered
2
2
2 n
(CO)6–nL
Os (ꢀ-pivalate) (CO) (PPh ) contains the largest average
according to the list of complexes in Table 5. Error bars represent twice
the s.u. values for both distances and angles.
2
2
4
3 2
ꢂ
C —Os—Os—C torsion angle (25 ) and the shortest Os—
eq eq
ꢃ
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˚
Os bond length (2.7198 A) of any Os sawhorse complex to
date (Chor et al., 2016).
Chor, B. Y., Ganguly, R. & Leong, W. K. (2016). J. Organomet. Chem.
2
804, 114–117.
Crooks, G. R., Johnson, B. F. G., Lewis, J., Williams, I. G. & Gamlen,
G. (1969). J. Chem. Soc. A, pp. 2761–2766.
Deeming, A. J., Randle, N. P., Hursthouse, M. B. & Short, R. L.
Acknowledgements
(1987). J. Chem. Soc. Dalton Trans. pp. 2473–2477.
We are grateful to Dr Joseph Reibenspies of Texas A&M
University and Professor Michael Richmond of the Univeristy
of North Texas for helpful discussions.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. &
Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
Fikes, A. G., Gwini, N., Yoon, S. H., Nesterov, V. N. & Powell, G. L.
(2014). J. Organomet. Chem. 772–773, 188–191.
Gwini, N., Marolf, D. M., Yoon, S. H., Fikes, A. G., Dugan, A. C.,
Powell, G. L., Lynch, V. M., Nesterov, V. N. & McCandless, G. T.
Funding information
(
2017). J. Organomet. Chem. 849–850, 324–331.
Funding for this research was provided by: The Welch Foun-
dation (grant No. R-0021) and the ACU Office of Under-
graduate Research.
Higashi, T. (2001). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Pyper, K. J., Jung, J. Y., Newton, B. S., Nesterov, V. N. & Powell, G. L.
(2013). J. Organomet. Chem. 723, 103–107.
Rigaku (2008). CrystalClear. Rigaku Inc., The Woodlands, Texas,
USA.
Rigaku OD (2015). CrysAlis PRO. Rigaku Corporation, Tokyo,
Japan.
Rigaku OD (2017). CrysAlis PRO. Rigaku Corporation, Tokyo,
Japan.
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Asymmetric diosmium sawhorse complexes 9 of 9

supporting information
supporting information
Acta Cryst. (2019). C75 [https://doi.org/10.1107/S2053229619004236]
Asymmetric diosmium sawhorse complexes
Kylie M. Wilson, John W. Swartout, Henry A. Touchton, Erica N. Lambert, James E. Johnstone,
Ashley K. Archambeau, David M. Marolf, Emily R. Mikeska, Vincent M. Lynch, Vladimir N.
Nesterov, Eric W. Reinheimer, Gregory L. Powell and Cynthia B. Powell
Computing details
Data collection: CrysAlis PRO (Rigaku OD, 2017) for 1@CH2Cl2, 4@1.5C8H10; APEX2 (Bruker, 2009) for (2), (8);
CrystalClear (Rigaku, 2008) for (3), 7@CH2Cl2; CrysAlis PRO (Rigaku OD, 2015) for (5), (6). Cell refinement:
CrysAlis PRO (Rigaku OD, 2017) for 1@CH2Cl2, 4@1.5C8H10; SAINT (Bruker, 2009) for (2), (8); CrystalClear
(Rigaku, 2008) for (3), 7@CH2Cl2; CrysAlis PRO (Rigaku OD, 2015) for (5), (6). Data reduction: CrysAlis PRO
(Rigaku OD, 2017) for 1@CH2Cl2, 4@1.5C8H10; SAINT (Bruker, 2009) for (2), (8); CrystalClear (Rigaku, 2008) for
(3), 7@CH2Cl2; CrysAlis PRO (Rigaku OD, 2015) for (5), (6). Program(s) used to solve structure: SHELXT (Sheldrick,
2
2
4
015a) for 1@CH2Cl2, (2), (5), (6), (8); SIR97 (Altomare et al., 1999) for (3), 7@CH2Cl2; SHELXT2014 (Sheldrick,
015a) for 4@1.5C8H10. Program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b) for 1@CH2Cl2, (2),
@1.5C8H10, (5), (6), (8); SHELXL2013 (Sheldrick, 2015a) for (3); SHELXL2013 (Sheldrick, 2013) for 7@CH2Cl2.
Molecular graphics: OLEX2 (Dolomanov et al., 2009) for 1@CH2Cl2, (2), 4@1.5C8H10, (5), (6), (8); XP in
SHELXTL/PC (Sheldrick, 1990) for (3), 7@CH2Cl2. Software used to prepare material for publication: OLEX2
(
Dolomanov et al., 2009) for 1@CH2Cl2, (2), 4@1.5C8H10, (5), (6), (8); XP in SHELXTL/PC (Sheldrick, 1990) for (3),
@CH2Cl2.
7
µ-Acetato-1κO:2κO′-µ-propanoato-1κO:2κO′-bis[tris(4-methylphenyl)phosphane]-1κP,2κP′-
bis(dicarbonylosmium)(Os—Os) dichloromethane monosolvate (1@CH2Cl2)
Crystal data
[
M
Os
= 1318.17
Monoclinic, P2
2
(C
2
H
3
O
2
)(C
3
H
5
O
)(C21H21P) (CO) ]·CH Cl
2 2 4 2 2
F(000) = 2576
= 1.725 Mg m
−3
r
D
x
1
/c
Cu Kα radiation, λ = 1.54184 Å
Cell parameters from 12326 reflections
θ = 4.5–73.3°
a = 18.5007 (4) Å
b = 18.5396 (4) Å
c = 14.8090 (3) Å
β = 91.9976 (17)°
V = 5076.35 (18) Å
Z = 4
−1
µ = 11.30 mm
T = 100 K
3
Plank, colorless
0.22 × 0.06 × 0.03 mm
Data collection
Rigaku SuperNova AtlasS2 CCD
diffractometer
Detector resolution: 5.2387 pixels mm
Absorption correction: gaussian
(CrysAlis PRO; Rigaku OD, 2017)
Tmin = 0.428, Tmax = 1.000
-1
ω scans
20129 measured reflections
265 independent reflections
9
Acta Cryst. (2019). C75
sup-1

supporting information
8
R
475 reflections with I > 2σ(I)
int = 0.024
h = −21→22
k = −19→22
l = −17→14
θ
max = 68.3°, θmin = 5.6°
Refinement
2
Refinement on F
Hydrogen site location: inferred from
neighbouring sites
Least-squares matrix: full
R[F > 2σ(F )] = 0.023
2
2
H-atom parameters constrained
2
2
2
2
wR(F ) = 0.055
w = 1/[σ (F
o
) + (0.0214P) + 5.3085P]
2
2
S = 1.00
where P = (F
o
+ 2F )/3
c
9
6
265 reflections
32 parameters
(Δ/σ)max = 0.002
Δρmax = 1.16 e Å
Δρmin = −1.05 e Å
−
3
−
3
112 restraints
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
Occ. (<1)
Os1
Os2
P1
P2
O1
O2
O3
O4
O5
O6
O7
O8
C1
C2
C3
C4
C5
0.24602 (2)
0.23338 (2)
0.25891 (4)
0.21444 (4)
0.39063 (12)
0.17142 (14)
0.36509 (14)
0.14255 (14)
0.28772 (13)
0.29035 (13)
0.14672 (11)
0.14444 (12)
0.33496 (17)
0.20033 (16)
0.31432 (18)
0.17734 (17)
0.29965 (17)
0.12202 (15)
0.29294 (16)
0.28798 (17)
0.243680
0.48548 (2)
0.49256 (2)
0.50855 (4)
0.53185 (4)
0.41219 (15)
0.34201 (14)
0.40392 (17)
0.35845 (14)
0.59099 (13)
0.59111 (14)
0.54428 (13)
0.55903 (14)
0.44046 (18)
0.39689 (19)
0.4387 (2)
0.40972 (19)
0.62065 (17)
0.57186 (17)
0.56904 (16)
0.58869 (19)
0.581524
0.6185 (2)
0.631017
0.63028 (18)
0.6085 (2)
0.614585
0.15721 (2)
0.34230 (2)
−0.00045 (5)
0.49394 (5)
0.17787 (16)
0.13616 (17)
0.39324 (17)
0.35453 (16)
0.17664 (14)
0.32777 (15)
0.15336 (14)
0.30353 (14)
0.16955 (19)
0.1439 (2)
0.3731 (2)
0.3493 (2)
0.2519 (2)
0.2239 (2)
0.5577 (2)
0.6477 (2)
0.677009
0.01357 (4)
0.01296 (4)
0.01549 (15)
0.01377 (14)
0.0266 (5)
0.0276 (5)
0.0354 (6)
0.0290 (5)
0.0217 (5)
0.0253 (5)
0.0211 (5)
0.0220 (5)
0.0187 (6)
0.0204 (7)
0.0221 (7)
0.0210 (7)
0.0218 (6)
0.0188 (6)
0.0152 (6)
0.0206 (7)
0.025*
C8
C10
C11
H11
C12
H12
C13
C14
H14
C15
0.34607 (17)
0.341304
0.41184 (16)
0.41764 (17)
0.462308
0.6957 (2)
0.757372
0.6541 (2)
0.5653 (2)
0.536482
0.0214 (7)
0.026*
0.0190 (6)
0.0222 (7)
0.027*
0.35921 (17)
0.57797 (19)
0.5174 (2)
0.0218 (7)
Acta Cryst. (2019). C75
sup-2

supporting information
H15
C16
H16A
H16B
H16C
C17
C18
H18
C19
H19
C20
C21
H21
C22
H22
C23
H23A
H23B
H23C
C24
C25
H25
C26
H26
C27
C28
H28
C29
H29
C30
H30A
H30B
H30C
C31
C32
H32
C33
H33
C34
C35
H35
C36
H36
C37
0.364641
0.47439 (17)
0.470386
0.520114
0.473149
0.563058
0.6672 (2)
0.719545
0.650346
0.655727
0.60298 (17)
0.58515 (19)
0.536103
0.6382 (2)
0.624888
0.7107 (2)
0.72843 (19)
0.777660
0.67526 (19)
0.688563
0.456666
0.7040 (2)
0.695725
0.680050
0.768528
0.49880 (19)
0.4842 (2)
0.475853
0.4817 (2)
0.472896
0.4918 (2)
0.5041 (2)
0.510092
0.5079 (2)
0.516747
0.4890 (3)
0.541756
0.433694
0.489889
0.5708 (2)
0.5619 (2)
0.512623
0.6231 (2)
0.614533
0.6974 (2)
0.7069 (2)
0.757079
0.6441 (2)
0.650930
0.7678 (2)
0.742620
0.820513
0.786020
−0.0201 (2)
−0.0017 (2)
0.016272
−0.0092 (3)
0.002209
−0.0335 (2)
−0.0506 (2)
−0.067077
−0.0440 (2)
−0.055853
−0.0398 (3)
0.021061
−0.075331
−0.069177
−0.0719 (2)
0.026*
0.0244 (7)
0.037*
0.037*
0.037*
0.0154 (6)
0.0206 (6)
0.025*
0.0227 (7)
0.027*
0.0223 (7)
0.0235 (7)
0.028*
0.0204 (6)
0.024*
0.14668 (16)
0.07374 (17)
0.060220
0.02107 (17)
−0.028264
0.03913 (18)
0.11192 (19)
0.125531
0.16513 (17)
0.214458
−0.0188 (2)
−0.049023
−0.048956
0.003800
0.18198 (15)
0.20280 (16)
0.231485
0.18271 (16)
0.196732
0.14207 (16)
0.12092 (17)
0.093335
0.13952 (16)
0.123336
0.7680 (2)
0.762871
0.762628
0.0327 (8)
0.049*
0.049*
0.815822
0.049*
0.46346 (18)
0.39197 (18)
0.378490
0.33976 (18)
0.291015
0.35819 (19)
0.42973 (19)
0.443309
0.48160 (17)
0.529865
0.0157 (6)
0.0173 (6)
0.021*
0.0180 (6)
0.022*
0.0197 (6)
0.0200 (6)
0.024*
0.0175 (6)
0.021*
0.1246 (2)
0.088624
0.105160
0.3029 (2)
0.268937
0.327067
0.0283 (8)
0.042*
0.042*
0.168693
0.276563
0.042*
0.33106 (17)
0.32189 (18)
0.276132
0.3785 (2)
0.370747
0.4469 (2)
0.45630 (17)
0.502391
0.39947 (16)
0.407204
0.5092 (2)
0.524938
0.493568
0.549566
0.28317 (16)
0.57266 (19)
0.6459 (2)
0.662835
0.6941 (2)
0.743849
0.6705 (2)
0.5974 (2)
0.580222
0.54921 (19)
0.499497
0.7229 (3)
0.738388
0.765050
0.699297
0.43215 (18)
0.0186 (6)
0.0253 (7)
0.030*
0.0325 (8)
0.039*
0.0291 (8)
0.0254 (7)
0.030*
0.0199 (6)
0.024*
0.0418 (10)
0.063*
0.063*
0.063*
0.0182 (6)
H37A
H37B
H37C
C38
Acta Cryst. (2019). C75
sup-3

supporting information
C39
H39
C40
H40
C41
C42
H42
C43
H43
C44
H44A
H44B
H44C
C45
C46
H46
C47
H47
0.29060 (16)
0.281898
0.31044 (17)
0.315867
0.32270 (17)
0.31542 (19)
0.323761
0.29603 (18)
0.291638
0.44399 (19)
0.490645
0.3884 (2)
0.397591
0.3190 (2)
0.3075 (2)
0.260721
0.3638 (2)
0.354882
0.2582 (2)
0.239353
0.219575
0.275952
0.54470 (18)
0.59718 (19)
0.619892
0.6165 (2)
0.652924
0.5835 (2)
0.5325 (2)
0.510349
0.51307 (19)
0.478064
0.6020 (2)
0.563639
0.606502
0.647717
0.7001 (3)
0.714118
0.713084
0.6216 (7)
0.607821
0.620471
0.7378 (6)
0.725351
0.790100
0.721881
0.6989 (4)
0.698975
0.734591
0.711250
0.6299 (7)
0.676991
0.629016
0.621372
0.6948 (3)
0.713028
0.727181
−0.1646 (2)
−0.189198
−0.2204 (2)
−0.282905
−0.1872 (2)
−0.0951 (2)
−0.070694
−0.0380 (2)
0.024786
−0.2490 (3)
−0.279777
−0.213472
−0.293940
−0.0635 (2)
−0.1303 (2)
−0.140735
−0.1818 (2)
−0.226577
−0.1689 (2)
−0.1011 (2)
−0.090312
−0.0485 (2)
−0.002159
−0.2291 (3)
−0.225184
−0.291712
−0.209418
0.2532 (14)
0.199177
0.307904
0.211 (2)
0.250609
0.147180
0.2532 (8)
0.197841
0.256045
0.305863
0.2361 (5)
0.299141
0.228465
0.196543
0.214 (2)
0.210375
0.266930
0.159332
0.2543 (14)
0.316480
0.215434
0.0198 (6)
0.024*
0.0228 (7)
0.027*
0.0243 (7)
0.0268 (7)
0.032*
0.0239 (7)
0.029*
0.3426 (2)
0.298789
0.366032
0.0353 (9)
0.053*
0.053*
0.375911
0.053*
0.17989 (16)
0.18411 (17)
0.229091
0.12309 (19)
0.126739
0.05649 (18)
0.05235 (17)
0.007187
0.11293 (17)
0.108708
−0.0085 (2)
−0.044745
0.006362
−0.029325
0.3157 (7)
0.342512
0.345090
0.0584 (7)
0.018924
0.039896
0.2419 (6)
0.214154
0.249011
0.215462
0.0886 (4)
0.106583
0.049730
0.128106
0.0655 (7)
0.089199
0.0176 (6)
0.0213 (7)
0.026*
0.0247 (7)
0.030*
0.0251 (7)
0.0234 (7)
0.028*
0.0194 (6)
0.023*
0.0339 (9)
0.051*
0.051*
0.051*
0.0286 (17)
0.034*
0.034*
0.0189 (16)
0.023*
0.023*
0.063 (2)
0.095*
0.095*
0.095*
0.0257 (13)
0.039*
0.039*
C48
C49
H49
C50
H50
C51
H51A
H51B
H51C
C6
H6A
H6B
C6A
H6AA
H6AB
C7
H7A
H7B
H7C
C7A
H7AA
H7AB
H7AC
C9
H9A
H9B
H9C
C9A
H9AA
H9AB
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.039*
0.021 (2)
0.031*
0.031*
0.031*
0.033 (2)
0.050*
0.050*
0.034882
0.035730
0.3324 (6)
0.333486
0.303331
Acta Cryst. (2019). C75
sup-4

supporting information
H9AC
Cl1
Cl2
C1S
H1SA
H1SB
0.381832
0.48305 (6)
0.53460 (8)
0.5169 (2)
0.481463
0.692543
0.58572 (8)
0.58296 (8)
0.5330 (2)
0.494723
0.509281
0.232696
0.18071 (9)
0.37000 (8)
0.2713 (3)
0.284202
0.253386
0.050*
0.5
0.0549 (3)
0.0608 (3)
0.0395 (9)
0.047*
0.562162
0.047*
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
Os1
Os2
P1
0.01404 (7)
0.01369 (7)
0.0169 (3)
0.01543 (8)
0.01444 (7)
0.0175 (4)
0.01151 (7)
0.01095 (7)
0.0124 (3)
0.00011 (5)
0.00000 (5)
0.0012 (3)
0.00434 (4)
0.00317 (4)
0.0049 (3)
−0.00057 (5)
−0.00072 (4)
0.0001 (3)
P2
O1
O2
O3
O4
O5
O6
O7
O8
C1
C2
C3
C4
C5
C8
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
0.0151 (3)
0.0143 (4)
0.0121 (3)
−0.0008 (3)
0.0080 (10)
−0.0090 (11)
0.0224 (13)
−0.0141 (11)
−0.0033 (9)
−0.0097 (10)
0.0079 (9)
0.0034 (2)
0.0039 (9)
0.0077 (10)
−0.0002 (10)
−0.0018 (10)
0.0062 (9)
0.0047 (9)
0.0044 (8)
0.0043 (8)
−0.0010 (3)
0.0033 (10)
−0.0056 (10)
−0.0031 (12)
0.0025 (10)
0.0000 (8)
−0.0003 (9)
0.0002 (9)
0.0005 (9)
0.0203 (11)
0.0334 (13)
0.0286 (13)
0.0401 (14)
0.0304 (11)
0.0334 (12)
0.0204 (10)
0.0236 (10)
0.0218 (15)
0.0169 (14)
0.0264 (16)
0.0207 (15)
0.0217 (14)
0.0170 (12)
0.0164 (13)
0.0176 (14)
0.0216 (15)
0.0176 (14)
0.0167 (14)
0.0221 (15)
0.0200 (15)
0.0176 (14)
0.0209 (15)
0.0161 (14)
0.0275 (17)
0.0300 (17)
0.0192 (14)
0.0331 (18)
0.0144 (13)
0.0166 (14)
0.0195 (14)
0.0174 (14)
0.0215 (14)
0.0211 (14)
0.0335 (14)
0.0205 (13)
0.0515 (18)
0.0239 (14)
0.0176 (11)
0.0223 (12)
0.0292 (13)
0.0280 (13)
0.0235 (17)
0.0287 (19)
0.0301 (19)
0.0274 (19)
0.0228 (15)
0.0218 (14)
0.0123 (14)
0.0292 (18)
0.0292 (19)
0.0178 (16)
0.0308 (19)
0.0274 (18)
0.0319 (19)
0.0177 (16)
0.0207 (17)
0.0316 (19)
0.0259 (18)
0.0179 (17)
0.0211 (17)
0.031 (2)
0.0263 (12)
0.0295 (13)
0.0260 (13)
0.0227 (12)
0.0176 (10)
0.0204 (11)
0.0140 (10)
0.0144 (10)
0.0112 (14)
0.0157 (15)
0.0102 (14)
0.0150 (15)
0.0213 (13)
0.0178 (13)
0.0170 (14)
0.0155 (15)
0.0137 (14)
0.0214 (15)
0.0194 (15)
0.0163 (15)
0.0210 (16)
0.0112 (13)
0.0204 (15)
0.0206 (15)
0.0138 (15)
0.0225 (16)
0.0211 (16)
0.034 (2)
0.0109 (9)
−0.0058 (13)
0.0035 (13)
−0.0017 (14)
0.0039 (14)
−0.0045 (12)
0.0010 (11)
0.0011 (11)
−0.0015 (13)
−0.0021 (13)
0.0003 (12)
−0.0034 (13)
−0.0023 (13)
−0.0016 (14)
0.0013 (12)
−0.0020 (13)
0.0049 (13)
0.0086 (14)
0.0029 (14)
−0.0012 (13)
0.0141 (16)
−0.0024 (12)
−0.0005 (12)
0.0022 (12)
−0.0021 (13)
−0.0039 (13)
0.0007 (12)
0.0052 (11)
0.0049 (11)
0.0037 (12)
0.0015 (11)
0.0070 (11)
0.0031 (10)
0.0009 (11)
0.0068 (11)
0.0041 (12)
0.0000 (12)
0.0043 (12)
0.0058 (12)
−0.0011 (12)
0.0044 (11)
0.0038 (12)
0.0006 (11)
0.0038 (12)
0.0024 (13)
0.0034 (12)
0.0027 (15)
0.0001 (10)
0.0017 (11)
0.0020 (11)
0.0026 (11)
0.0084 (11)
0.0032 (11)
−0.0006 (12)
−0.0005 (13)
−0.0056 (13)
0.0001 (13)
0.0020 (12)
0.0017 (11)
0.0013 (11)
−0.0009 (13)
−0.0009 (13)
0.0003 (12)
−0.0019 (13)
−0.0045 (13)
−0.0046 (14)
0.0005 (11)
−0.0024 (13)
−0.0021 (14)
−0.0020 (13)
0.0003 (13)
0.0003 (13)
−0.0015 (16)
0.0004 (12)
−0.0012 (12)
0.0016 (12)
0.0032 (13)
0.0001 (12)
−0.0025 (12)
0.0179 (16)
0.0203 (16)
0.0160 (15)
0.0246 (17)
0.0229 (17)
0.0161 (15)
0.0149 (14)
0.0150 (14)
0.0185 (15)
0.0173 (15)
0.0163 (14)
0.0155 (14)
Acta Cryst. (2019). C75
sup-5

supporting information
C30
C31
C32
C33
C34
C35
C36
C37
C38
C39
C40
C41
C42
C43
C44
C45
C46
C47
C48
C49
C50
C51
C6
0.0313 (18)
0.0192 (14)
0.0227 (16)
0.036 (2)
0.0285 (17)
0.0181 (15)
0.0191 (14)
0.035 (2)
0.0144 (13)
0.0176 (14)
0.0194 (15)
0.0199 (15)
0.0335 (18)
0.0259 (16)
0.040 (2)
0.0193 (14)
0.0222 (15)
0.0291 (17)
0.0235 (16)
0.0189 (14)
0.0202 (14)
0.0270 (17)
0.036 (4)
0.0267 (19)
0.0238 (17)
0.0243 (18)
0.027 (2)
0.036 (2)
0.039 (2)
0.0276 (18)
0.0130 (14)
0.0298 (18)
0.035 (2)
0.0235 (17)
0.0198 (16)
0.0154 (14)
0.046 (2)
0.0175 (15)
0.0180 (15)
0.0158 (15)
0.0233 (17)
0.0261 (18)
0.0202 (16)
0.0268 (19)
0.0143 (14)
0.0203 (15)
0.0206 (16)
0.0209 (16)
0.0198 (15)
0.0116 (14)
0.0293 (19)
0.027 (3)
0.0020 (15)
−0.0009 (13)
−0.0013 (14)
−0.0071 (16)
−0.0094 (16)
−0.0037 (14)
0.0031 (13)
−0.0175 (19)
0.0011 (12)
0.0022 (12)
0.0035 (14)
0.0059 (14)
0.0065 (14)
0.0049 (14)
0.0196 (18)
0.0038 (12)
0.0034 (13)
0.0087 (14)
0.0086 (14)
0.0004 (14)
0.0024 (13)
0.0083 (17)
−0.012 (3)
0.003 (2)
0.0097 (14)
0.0046 (11)
0.0120 (13)
0.0158 (16)
0.0093 (14)
0.0052 (12)
0.0039 (11)
0.0157 (18)
0.0037 (11)
0.0017 (11)
0.0012 (12)
−0.0012 (12)
0.0022 (14)
0.0046 (12)
−0.0029 (15)
0.0046 (11)
0.0080 (12)
0.0062 (13)
0.0005 (13)
0.0060 (12)
0.0047 (11)
−0.0011 (14)
0.005 (4)
0.0102 (15)
0.0004 (12)
−0.0014 (14)
−0.0067 (16)
−0.0027 (15)
0.0003 (14)
−0.0001 (12)
−0.008 (2)
−0.0046 (12)
0.0000 (13)
−0.0054 (13)
−0.0074 (14)
−0.0035 (14)
0.0000 (14)
−0.0118 (16)
−0.0016 (12)
0.0009 (13)
0.0022 (13)
−0.0056 (14)
−0.0065 (14)
−0.0020 (12)
0.0026 (17)
0.001 (2)
0.0253 (17)
0.045 (3)
0.0227 (17)
0.0239 (17)
0.033 (2)
0.0294 (19)
0.0208 (18)
0.0259 (18)
0.039 (2)
0.0196 (16)
0.0220 (17)
0.0248 (18)
0.0309 (19)
0.0318 (19)
0.0267 (18)
0.045 (2)
0.023 (3)
0.021 (3)
0.042 (4)
C6A
C7
0.018 (3)
0.071 (5)
0.018 (3)
0.077 (5)
0.001 (3)
0.019 (5)
−0.002 (3)
−0.001 (4)
0.008 (4)
C7A
C9
C9A
Cl1
Cl2
C1S
0.030 (3)
0.017 (3)
0.043 (5)
0.0407 (5)
0.0862 (9)
0.045 (2)
0.020 (3)
0.026 (4)
0.021 (3)
0.0619 (8)
0.0585 (8)
0.030 (2)
0.027 (3)
0.019 (4)
0.036 (4)
0.0615 (7)
0.0396 (6)
0.044 (2)
0.004 (2)
0.004 (3)
−0.008 (3)
0.0047 (5)
−0.0064 (7)
−0.0006 (18)
0.000 (3)
−0.001 (3)
0.020 (5)
−0.0063 (5)
0.0283 (6)
0.0034 (18)
−0.003 (3)
−0.002 (4)
−0.005 (3)
0.0222 (6)
−0.0143 (5)
0.0017 (18)
Geometric parameters (Å, º)
Os1—Os2
Os1—P1
Os1—O5
Os1—O7
Os1—C1
Os1—C2
Os2—P2
Os2—O6
Os2—O8
Os2—C3
Os2—C4
P1—C31
P1—C38
P1—C45
2.7623 (2)
C30—H30A
0.9800
0.9800
0.9800
2.3937 (7)
2.119 (2)
2.135 (2)
1.848 (3)
1.854 (4)
2.3981 (7)
2.124 (2)
2.119 (2)
1.844 (3)
1.858 (4)
1.818 (3)
1.833 (3)
1.834 (3)
C30—H30B
C30—H30C
C31—C32
C31—C36
C32—H32
C32—C33
C33—H33
C33—C34
C34—C35
C34—C37
C35—H35
C35—C36
C36—H36
1.396 (5)
1.395 (4)
0.9500
1.384 (5)
0.9500
1.398 (5)
1.390 (6)
1.514 (5)
0.9500
1.386 (5)
0.9500
Acta Cryst. (2019). C75
sup-6

supporting information
P2—C10
P2—C17
P2—C24
O1—C1
O2—C2
O3—C3
O4—C4
O5—C5
O6—C5
O7—C8
O8—C8
C5—C6
C5—C9A
C8—C6A
C8—C9
C10—C11
C10—C15
C11—H11
C11—C12
C12—H12
C12—C13
C13—C14
C13—C16
C14—H14
C14—C15
C15—H15
C16—H16A
C16—H16B
C16—H16C
C17—C18
C17—C22
C18—H18
C18—C19
C19—H19
C19—C20
C20—C21
C20—C23
C21—H21
C21—C22
C22—H22
C23—H23A
C23—H23B
C23—H23C
C24—C25
C24—C29
C25—H25
C25—C26
C26—H26
1.839 (3)
1.823 (3)
1.820 (3)
1.158 (4)
1.153 (4)
1.169 (4)
1.152 (4)
1.255 (4)
1.268 (4)
1.263 (4)
1.259 (4)
1.502 (4)
1.502 (4)
1.502 (4)
1.502 (4)
1.388 (4)
1.392 (4)
0.9500
1.382 (5)
0.9500
1.400 (4)
1.383 (5)
1.515 (4)
0.9500
1.393 (5)
0.9500
0.9800
C37—H37A
C37—H37B
C37—H37C
C38—C39
C38—C43
C39—H39
C39—C40
C40—H40
C40—C41
C41—C42
C41—C44
C42—H42
C42—C43
C43—H43
C44—H44A
C44—H44B
C44—H44C
C45—C46
C45—C50
C46—H46
C46—C47
C47—H47
C47—C48
C48—C49
C48—C51
C49—H49
C49—C50
C50—H50
C51—H51A
C51—H51B
C51—H51C
C6—H6A
0.9800
0.9800
0.9800
1.402 (4)
1.382 (5)
0.9500
1.379 (5)
0.9500
1.393 (5)
1.392 (5)
1.506 (5)
0.9500
1.398 (5)
0.9500
0.9800
0.9800
0.9800
1.392 (5)
1.395 (5)
0.9500
1.387 (5)
0.9500
1.395 (5)
1.384 (5)
1.510 (5)
0.9500
1.390 (5)
0.9500
0.9800
0.9800
0.9800
0.9900
0.9900
1.533 (17)
0.9900
0.9900
1.579 (18)
0.9800
0.9800
0.9800
1.399 (4)
1.388 (5)
0.9500
1.384 (5)
0.9500
1.392 (5)
1.392 (5)
1.510 (5)
0.9500
1.393 (5)
0.9500
0.9800
0.9800
0.9800
1.388 (5)
1.404 (4)
0.9500
1.386 (4)
0.9500
C6—H6B
C6—C7
C6A—H6AA
C6A—H6AB
C6A—C7A
C7—H7A
C7—H7B
C7—H7C
C7A—H7AA
C7A—H7AB
C7A—H7AC
C9—H9A
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
C9—H9B
C9—H9C
C9A—H9AA
C9A—H9AB
0.9800
0.9800
Acta Cryst. (2019). C75
sup-7

supporting information
C26—C27
C27—C28
C27—C30
C28—H28
C28—C29
C29—H29
1.396 (4)
1.391 (5)
1.505 (5)
0.9500
1.389 (5)
0.9500
C9A—H9AC
Cl1—C1S
Cl2—C1S
C1S—H1SA
C1S—H1SB
0.9800
1.758 (4)
1.751 (4)
0.9900
0.9900
P1—Os1—Os2
O5—Os1—Os2
O5—Os1—P1
O5—Os1—O7
O7—Os1—Os2
O7—Os1—P1
C1—Os1—Os2
C1—Os1—P1
C1—Os1—O5
C1—Os1—O7
C1—Os1—C2
C2—Os1—Os2
C2—Os1—P1
C2—Os1—O5
C2—Os1—O7
P2—Os2—Os1
O6—Os2—Os1
O6—Os2—P2
O8—Os2—Os1
O8—Os2—P2
O8—Os2—O6
C3—Os2—Os1
C3—Os2—P2
C3—Os2—O6
C3—Os2—O8
C3—Os2—C4
C4—Os2—Os1
C4—Os2—P2
C4—Os2—O6
C4—Os2—O8
C31—P1—Os1
C31—P1—C38
C31—P1—C45
C38—P1—Os1
C45—P1—Os1
C45—P1—C38
C10—P2—Os2
C17—P2—Os2
C17—P2—C10
C24—P2—Os2
C24—P2—C10
166.94 (2)
82.20 (6)
85.37 (6)
80.86 (9)
84.24 (6)
89.86 (6)
91.67 (9)
93.36 (9)
94.86 (12)
174.43 (11)
90.66 (14)
95.37 (9)
96.60 (10)
174.02 (11)
93.48 (12)
164.55 (2)
83.16 (6)
85.57 (6)
81.41 (6)
86.54 (6)
81.70 (10)
97.08 (9)
C24—C29—H29
C28—C29—C24
C28—C29—H29
C27—C30—H30A
C27—C30—H30B
C27—C30—H30C
H30A—C30—H30B
H30A—C30—H30C
H30B—C30—H30C
C32—C31—P1
119.7
120.7 (3)
119.7
109.5
109.5
109.5
109.5
109.5
109.5
120.6 (2)
118.0 (3)
121.0 (3)
119.5
121.0 (3)
119.5
119.6
120.8 (4)
119.6
120.9 (4)
118.2 (3)
121.0 (3)
119.5
121.0 (3)
119.5
119.5
120.9 (3)
119.5
109.5
109.5
109.5
109.5
109.5
109.5
118.6 (3)
122.8 (2)
118.6 (3)
119.8
120.5 (3)
119.8
C32—C31—C36
C36—C31—P1
C31—C32—H32
C33—C32—C31
C33—C32—H32
C32—C33—H33
C32—C33—C34
C34—C33—H33
C33—C34—C37
C35—C34—C33
C35—C34—C37
C34—C35—H35
C36—C35—C34
C36—C35—H35
C31—C36—H36
C35—C36—C31
C35—C36—H36
C34—C37—H37A
C34—C37—H37B
C34—C37—H37C
H37A—C37—H37B
H37A—C37—H37C
H37B—C37—H37C
C39—C38—P1
94.43 (9)
95.14 (13)
176.62 (13)
89.32 (15)
94.74 (9)
95.67 (10)
175.27 (12)
93.80 (12)
111.82 (10)
102.51 (14)
104.85 (15)
117.36 (11)
117.19 (10)
101.28 (14)
117.15 (10)
112.33 (10)
103.91 (14)
115.85 (10)
102.25 (13)
C43—C38—P1
C43—C38—C39
C38—C39—H39
C40—C39—C38
C40—C39—H39
C39—C40—H40
C39—C40—C41
119.2
121.5 (3)
Acta Cryst. (2019). C75
sup-8

supporting information
C24—P2—C17
C5—O5—Os1
C5—O6—Os2
C8—O7—Os1
C8—O8—Os2
O1—C1—Os1
O2—C2—Os1
O3—C3—Os2
O4—C4—Os2
103.71 (14)
125.2 (2)
123.0 (2)
121.36 (19)
126.24 (19)
179.6 (3)
179.3 (3)
179.1 (3)
179.3 (3)
124.9 (3)
118.0 (8)
118.7 (9)
116.4 (8)
116.2 (9)
116.4 (12)
118.8 (12)
125.5 (3)
118.0 (12)
115.4 (11)
120.9 (2)
118.0 (3)
121.1 (2)
119.3
121.5 (3)
119.3
119.7
120.6 (3)
119.7
121.2 (3)
118.0 (3)
120.8 (3)
119.4
121.2 (3)
119.4
120.7 (3)
119.7
119.7
109.5
C41—C40—H40
C40—C41—C44
C42—C41—C40
C42—C41—C44
C41—C42—H42
C41—C42—C43
C43—C42—H42
C38—C43—C42
C38—C43—H43
C42—C43—H43
C41—C44—H44A
C41—C44—H44B
C41—C44—H44C
H44A—C44—H44B
H44A—C44—H44C
H44B—C44—H44C
C46—C45—P1
119.2
121.2 (3)
117.9 (3)
121.0 (3)
119.5
121.0 (3)
119.5
120.6 (3)
119.7
119.7
109.5
109.5
109.5
109.5
O5—C5—O6
O5—C5—C6
O5—C5—C9A
O6—C5—C6
O6—C5—C9A
O7—C8—C6A
O7—C8—C9
O8—C8—O7
O8—C8—C6A
O8—C8—C9
109.5
109.5
123.6 (2)
118.6 (3)
117.5 (2)
119.8
120.5 (3)
119.8
119.4
121.2 (3)
119.4
120.6 (3)
118.1 (3)
121.3 (3)
119.3
121.4 (3)
119.3
119.8
120.3 (3)
119.8
109.5
109.5
109.5
109.5
109.5
109.5
110.6
110.6
C46—C45—C50
C50—C45—P1
C11—C10—P2
C11—C10—C15
C15—C10—P2
C10—C11—H11
C12—C11—C10
C12—C11—H11
C11—C12—H12
C11—C12—C13
C13—C12—H12
C12—C13—C16
C14—C13—C12
C14—C13—C16
C13—C14—H14
C13—C14—C15
C15—C14—H14
C10—C15—C14
C10—C15—H15
C14—C15—H15
C13—C16—H16A
C13—C16—H16B
C13—C16—H16C
H16A—C16—H16B
H16A—C16—H16C
H16B—C16—H16C
C18—C17—P2
C22—C17—P2
C22—C17—C18
C17—C18—H18
C19—C18—C17
C45—C46—H46
C47—C46—C45
C47—C46—H46
C46—C47—H47
C46—C47—C48
C48—C47—H47
C47—C48—C51
C49—C48—C47
C49—C48—C51
C48—C49—H49
C48—C49—C50
C50—C49—H49
C45—C50—H50
C49—C50—C45
C49—C50—H50
C48—C51—H51A
C48—C51—H51B
C48—C51—H51C
H51A—C51—H51B
H51A—C51—H51C
H51B—C51—H51C
C5—C6—H6A
109.5
109.5
109.5
109.5
C5—C6—H6B
C5—C6—C7
H6A—C6—H6B
C7—C6—H6A
C7—C6—H6B
109.5
105.7 (8)
108.7
110.6
110.6
110.8
118.9 (3)
122.3 (2)
118.4 (3)
119.6
C8—C6A—H6AA
C8—C6A—H6AB
120.7 (3)
110.8
Acta Cryst. (2019). C75
sup-9

supporting information
C19—C18—H18
C18—C19—H19
C18—C19—C20
C20—C19—H19
C19—C20—C23
C21—C20—C19
C21—C20—C23
C20—C21—H21
C20—C21—C22
C22—C21—H21
C17—C22—C21
C17—C22—H22
C21—C22—H22
C20—C23—H23A
C20—C23—H23B
C20—C23—H23C
H23A—C23—H23B
H23A—C23—H23C
H23B—C23—H23C
C25—C24—P2
119.6
119.4
C8—C6A—C7A
105.0 (9)
H6AA—C6A—H6AB
C7A—C6A—H6AA
C7A—C6A—H6AB
C6—C7—H7A
C6—C7—H7B
C6—C7—H7C
H7A—C7—H7B
H7A—C7—H7C
H7B—C7—H7C
C6A—C7A—H7AA
C6A—C7A—H7AB
C6A—C7A—H7AC
H7AA—C7A—H7AB
H7AA—C7A—H7AC
H7AB—C7A—H7AC
C8—C9—H9A
C8—C9—H9B
C8—C9—H9C
H9A—C9—H9B
H9A—C9—H9C
108.8
110.8
110.8
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
108.9
108.9
113.2 (3)
108.9
108.9
107.7
121.1 (3)
119.4
120.6 (3)
118.0 (3)
121.3 (3)
119.4
121.1 (3)
119.4
120.5 (3)
119.7
119.7
109.5
109.5
109.5
109.5
109.5
109.5
120.5 (2)
117.9 (3)
121.5 (2)
119.2
121.5 (3)
119.2
119.7
120.6 (3)
119.7
120.9 (3)
118.3 (3)
120.8 (3)
119.5
121.0 (3)
119.5
C25—C24—C29
C29—C24—P2
H9B—C9—H9C
C24—C25—H25
C26—C25—C24
C26—C25—H25
C25—C26—H26
C25—C26—C27
C27—C26—H26
C26—C27—C30
C28—C27—C26
C28—C27—C30
C27—C28—H28
C29—C28—C27
C29—C28—H28
C5—C9A—H9AA
C5—C9A—H9AB
C5—C9A—H9AC
H9AA—C9A—H9AB
H9AA—C9A—H9AC
H9AB—C9A—H9AC
Cl1—C1S—H1SA
Cl1—C1S—H1SB
Cl2—C1S—Cl1
Cl2—C1S—H1SA
Cl2—C1S—H1SB
H1SA—C1S—H1SB
Os1—P1—C31—C32
Os1—P1—C31—C36
Os1—P1—C38—C39
Os1—P1—C38—C43
Os1—P1—C45—C46
Os1—P1—C45—C50
Os1—O5—C5—O6
Os1—O5—C5—C6
Os1—O5—C5—C9A
Os1—O7—C8—O8
Os1—O7—C8—C6A
Os1—O7—C8—C9
Os2—P2—C10—C11
−73.8 (3)
98.8 (2)
179.6 (2)
−1.9 (3)
141.0 (2)
−44.7 (3)
2.0 (5)
−168.6 (6)
177.4 (6)
−12.2 (5)
170.6 (8)
162.1 (8)
−175.8 (2)
C17—C18—C19—C20
C18—C17—C22—C21
C18—C19—C20—C21
C18—C19—C20—C23
C19—C20—C21—C22
C20—C21—C22—C17
C22—C17—C18—C19
C23—C20—C21—C22
C24—P2—C10—C11
C24—P2—C10—C15
C24—P2—C17—C18
C24—P2—C17—C22
C24—C25—C26—C27
1.3 (5)
1.2 (5)
0.3 (5)
−180.0 (3)
−1.2 (5)
0.4 (5)
−2.0 (5)
179.1 (3)
−48.0 (3)
131.6 (3)
−52.3 (3)
134.1 (3)
−1.6 (5)
Acta Cryst. (2019). C75
sup-10

supporting information
Os2—P2—C10—C15
Os2—P2—C17—C18
Os2—P2—C17—C22
Os2—P2—C24—C25
Os2—P2—C24—C29
Os2—O6—C5—O5
Os2—O6—C5—C6
Os2—O6—C5—C9A
Os2—O8—C8—O7
Os2—O8—C8—C6A
Os2—O8—C8—C9
P1—C31—C32—C33
P1—C31—C36—C35
P1—C38—C39—C40
P1—C38—C43—C42
P1—C45—C46—C47
P1—C45—C50—C49
P2—C10—C11—C12
P2—C10—C15—C14
P2—C17—C18—C19
P2—C17—C22—C21
P2—C24—C25—C26
P2—C24—C29—C28
O5—C5—C6—C7
3.9 (3)
73.6 (2)
−100.1 (3)
33.0 (3)
−151.4 (2)
−12.3 (5)
158.4 (6)
172.2 (6)
3.7 (5)
−179.1 (8)
−170.7 (8)
174.5 (3)
−173.8 (2)
178.5 (2)
−179.0 (3)
173.2 (3)
−173.0 (3)
−178.3 (3)
177.7 (3)
−175.9 (2)
174.9 (2)
175.6 (2)
−173.9 (2)
86.2 (12)
−85.2 (12)
−111.4 (13)
71.2 (17)
−158.9 (2)
27.5 (3)
C25—C24—C29—C28
1.8 (4)
1.5 (5)
−175.6 (3)
0.2 (5)
C25—C26—C27—C28
C25—C26—C27—C30
C26—C27—C28—C29
C27—C28—C29—C24
C29—C24—C25—C26
C30—C27—C28—C29
C31—P1—C38—C39
C31—P1—C38—C43
C31—P1—C45—C46
C31—P1—C45—C50
C31—C32—C33—C34
C32—C31—C36—C35
C32—C33—C34—C35
C32—C33—C34—C37
C33—C34—C35—C36
C34—C35—C36—C31
C36—C31—C32—C33
C37—C34—C35—C36
C38—P1—C31—C32
C38—P1—C31—C36
C38—P1—C45—C46
C38—P1—C45—C50
C38—C39—C40—C41
C39—C38—C43—C42
C39—C40—C41—C42
C39—C40—C41—C44
C40—C41—C42—C43
C41—C42—C43—C38
C43—C38—C39—C40
C44—C41—C42—C43
C45—P1—C31—C32
C45—P1—C31—C36
C45—P1—C38—C39
C45—P1—C38—C43
C45—C46—C47—C48
C46—C45—C50—C49
C46—C47—C48—C49
C46—C47—C48—C51
C47—C48—C49—C50
C48—C49—C50—C45
C50—C45—C46—C47
C51—C48—C49—C50
−1.8 (5)
−0.1 (4)
177.3 (3)
−57.5 (3)
121.0 (3)
16.3 (3)
−169.4 (2)
−1.5 (6)
−1.0 (5)
0.6 (6)
−178.7 (4)
0.1 (5)
0.1 (5)
1.7 (5)
179.3 (3)
159.6 (3)
−27.8 (3)
−90.0 (3)
84.3 (3)
0.9 (5)
−0.5 (5)
−1.0 (5)
178.5 (3)
0.4 (5)
O6—C5—C6—C7
O7—C8—C6A—C7A
O8—C8—C6A—C7A
C10—P2—C17—C18
C10—P2—C17—C22
C10—P2—C24—C25
C10—P2—C24—C29
C10—C11—C12—C13
C11—C10—C15—C14
C11—C12—C13—C14
C11—C12—C13—C16
C12—C13—C14—C15
C13—C14—C15—C10
C15—C10—C11—C12
C16—C13—C14—C15
C17—P2—C10—C11
C17—P2—C10—C15
C17—P2—C24—C25
C17—P2—C24—C29
0.4 (5)
−95.6 (3)
80.0 (3)
0.6 (5)
−2.6 (5)
−2.7 (5)
176.0 (3)
2.1 (5)
0.6 (6)
2.1 (5)
−176.6 (3)
59.7 (3)
−0.1 (5)
−179.1 (3)
54.2 (3)
−133.2 (3)
50.7 (3)
−130.8 (3)
−0.9 (5)
1.6 (5)
2.2 (5)
−176.4 (3)
−1.6 (5)
−0.3 (5)
−1.1 (5)
176.9 (3)
−120.7 (3)
156.6 (2)
−27.9 (3)
Acta Cryst. (2019). C75
sup-11

supporting information
Bis(µ-acetato-1κO:2κO′)bis(tricarbonylosmium)(Os—Os) (2)
Crystal data
[
M
Os
= 666.55
Monoclinic, P2
2
(C
2
H
3
O
2
)
2
(CO)
6
]
F(000) = 1192
= 2.995 Mg m
−3
r
D
x
1
/n
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9606 reflections
θ = 2.8–33.1°
a = 7.6949 (5) Å
b = 14.3612 (10) Å
c = 13.8623 (9) Å
β = 105.202 (1)°
V = 1478.29 (17) Å
Z = 4
−1
µ = 17.22 mm
T = 200 K
3
Block, colorless
0.19 × 0.12 × 0.07 mm
Data collection
Bruker APEXII CCD
diffractometer
3252 independent reflections
3003 reflections with I > 2σ(I)
φ and ω scans
R
int = 0.046
Absorption correction: multi-scan
θmax = 27.1°, θmin = 2.1°
(
SADABS; Bruker, 2008)
h = −9→9
T
min = 0.295, Tmax = 0.747
k = −18→18
l = −17→17
1
4002 measured reflections
Refinement
2
Refinement on F
H-atom parameters constrained
2
2
2
Least-squares matrix: full
R[F > 2σ(F )] = 0.023
w = 1/[σ (F
where P = (F
o
) + (0.0082P) + 2.0911P]
2
2
2
2
o
+ 2F )/3
c
2
wR(F ) = 0.055
(Δ/σ)max = 0.001
Δρmax = 1.80 e Å
Δρmin = −1.33 e Å
−
3
S = 1.09
−
3
3
2
0
252 reflections
02 parameters
restraints
Extinction correction: SHELXL2018
(Sheldrick, 2015b),
*
2
3
-1/4
Hydrogen site location: inferred from
neighbouring sites
Fc =kFc[1+0.001xFc λ /sin(2θ)]
Extinction coefficient: 0.00198 (9)
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
Os1
Os2
O8
O9
O7
O10
O3
O2
0.42547 (2)
0.77231 (2)
0.6745 (4)
0.5294 (4)
0.4059 (4)
0.8002 (4)
0.0418 (5)
0.4741 (6)
0.8856 (6)
0.22664 (2)
0.21800 (2)
0.3123 (2)
0.3337 (2)
0.3352 (2)
0.3386 (2)
0.2846 (3)
0.0738 (3)
0.0922 (3)
0.05236 (2)
0.17010 (2)
0.2608 (2)
−0.0211 (2)
0.1523 (2)
0.0881 (2)
−0.0685 (3)
−0.0875 (3)
0.0236 (3)
0.01655 (7)
0.01619 (7)
0.0223 (7)
0.0239 (7)
0.0233 (7)
0.0253 (7)
0.0424 (10)
0.0430 (10)
0.0391 (9)
O4
Acta Cryst. (2019). C75
sup-12

supporting information
C7
O5
O1
O6
C4
C1
C5
C8
H8A
H8B
H8C
C9
C2
C3
0.5235 (6)
0.7127 (6)
0.3004 (6)
1.1610 (5)
0.8448 (6)
0.3453 (6)
0.7343 (6)
0.4787 (7)
0.579579
0.370674
0.456292
0.6840 (6)
0.4554 (7)
0.1837 (7)
1.0190 (7)
0.7308 (8)
0.830534
0.625795
0.766953
0.3522 (3)
0.0534 (3)
0.0859 (3)
0.2535 (4)
0.1390 (3)
0.1378 (3)
0.1147 (3)
0.4249 (3)
0.432174
0.406277
0.484157
0.3691 (3)
0.1320 (3)
0.2639 (3)
0.2415 (4)
0.4540 (4)
0.486855
0.495203
0.435746
0.2335 (3)
0.2927 (3)
0.1800 (3)
0.2995 (3)
0.0800 (3)
0.1300 (4)
0.2464 (3)
0.2994 (3)
0.358999
0.0190 (9)
0.0417 (9)
0.0462 (10)
0.0459 (10)
0.0262 (10)
0.0271 (10)
0.0243 (10)
0.0288 (10)
0.043*
0.319369
0.263170
0.043*
0.043*
0.0140 (3)
−0.0357 (3)
−0.0252 (4)
0.2537 (4)
−0.0362 (4)
0.009782
0.0211 (9)
0.0269 (10)
0.0260 (10)
0.0263 (10)
0.0350 (12)
0.053*
C6
C10
H10A
H10B
H10C
−0.055015
−0.096241
0.053*
0.053*
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
Os1
Os2
O8
O9
O7
O10
O3
O2
O4
C7
O5
O1
O6
C4
C1
C5
C8
C9
C2
C3
C6
C10
0.01386 (11)
0.01358 (11)
0.0225 (17)
0.0249 (17)
0.0233 (17)
0.0228 (17)
0.020 (2)
0.051 (2)
0.049 (2)
0.021 (2)
0.056 (3)
0.044 (2)
0.017 (2)
0.021 (2)
0.017 (2)
0.024 (2)
0.036 (3)
0.023 (2)
0.025 (2)
0.023 (3)
0.025 (3)
0.040 (3)
0.01834 (11)
0.01921 (11)
0.0263 (16)
0.0267 (17)
0.0236 (16)
0.0235 (17)
0.059 (3)
0.038 (2)
0.043 (2)
0.019 (2)
0.036 (2)
0.041 (2)
0.072 (3)
0.032 (3)
0.029 (3)
0.027 (2)
0.026 (2)
0.019 (2)
0.029 (2)
0.026 (2)
0.031 (2)
0.030 (3)
0.01733 (10)
0.01643 (10)
0.0179 (14)
0.0201 (14)
0.0233 (14)
0.0281 (16)
0.043 (2)
0.0347 (19)
0.0332 (18)
0.0194 (19)
0.0348 (19)
0.061 (3)
0.043 (2)
0.027 (2)
0.034 (2)
0.022 (2)
0.027 (2)
0.024 (2)
0.024 (2)
0.030 (2)
0.00051 (6)
0.00390 (6)
0.0063 (13)
−0.0001 (14)
0.0049 (13)
−0.0032 (13)
0.0106 (17)
0.0136 (19)
0.0186 (19)
−0.0005 (17)
−0.0006 (19)
−0.0100 (19)
−0.001 (2)
0.008 (2)
−0.0016 (19)
0.005 (2)
0.000 (2)
0.0017 (18)
0.003 (2)
−0.0003 (19)
0.004 (2)
0.00388 (7)
0.00506 (7)
0.0052 (12)
0.0058 (13)
0.0064 (13)
0.0042 (13)
−0.0002 (18)
0.0013 (17)
0.0241 (17)
0.0094 (17)
0.0159 (18)
0.026 (2)
−0.0022 (19)
0.0091 (19)
0.005 (2)
0.0078 (18)
0.014 (2)
−0.00074 (5)
0.00252 (5)
−0.0054 (12)
0.0088 (12)
−0.0021 (12)
0.0067 (13)
−0.0021 (17)
−0.0148 (16)
−0.0037 (16)
0.0012 (15)
0.0141 (16)
0.0172 (19)
0.007 (2)
0.0094 (19)
−0.0031 (19)
0.0005 (18)
−0.0064 (18)
0.0015 (16)
−0.0003 (18)
−0.0031 (18)
0.0021 (19)
0.010 (2)
0.0106 (18)
0.0008 (19)
0.009 (2)
0.012 (2)
0.014 (2)
0.025 (2)
0.038 (3)
−0.002 (2)
Acta Cryst. (2019). C75
sup-13

supporting information
Geometric parameters (Å, º)
Os1—Os2
Os1—O9
Os1—O7
Os1—C1
Os1—C2
Os1—C3
Os2—O8
Os2—O10
Os2—C4
Os2—C5
Os2—C6
O8—C7
2.7419 (3)
2.113 (3)
2.118 (3)
1.876 (5)
1.881 (5)
1.963 (5)
2.116 (3)
2.114 (3)
1.877 (5)
1.889 (5)
1.976 (5)
1.262 (5)
1.268 (5)
1.269 (5)
1.251 (5)
O3—C3
O2—C2
O4—C4
C7—C8
O5—C5
O1—C1
O6—C6
C8—H8A
C8—H8B
C8—H8C
C9—C10
C10—H10A
C10—H10B
C10—H10C
1.139 (6)
1.135 (6)
1.137 (6)
1.486 (6)
1.128 (6)
1.131 (6)
1.124 (7)
0.9800
0.9800
0.9800
1.494 (6)
0.9800
0.9800
O9—C9
O7—C7
O10—C9
0.9800
O9—Os1—Os2
O9—Os1—O7
O7—Os1—Os2
C1—Os1—Os2
C1—Os1—O9
C1—Os1—O7
C1—Os1—C2
C1—Os1—C3
C2—Os1—Os2
C2—Os1—O9
C2—Os1—O7
C2—Os1—C3
C3—Os1—Os2
C3—Os1—O9
C3—Os1—O7
O8—Os2—Os1
O10—Os2—Os1
O10—Os2—O8
C4—Os2—Os1
C4—Os2—O8
C4—Os2—O10
C4—Os2—C5
C4—Os2—C6
C5—Os2—Os1
C5—Os2—O8
C5—Os2—O10
C5—Os2—C6
C6—Os2—Os1
C6—Os2—O8
83.54 (8)
83.14 (13)
82.46 (8)
92.46 (14)
174.06 (16)
92.00 (17)
89.8 (2)
C6—Os2—O10
C7—O8—Os2
C9—O9—Os1
C7—O7—Os1
C9—O10—Os2
O8—C7—O7
87.60 (17)
123.7 (3)
122.9 (3)
124.4 (3)
125.3 (3)
124.4 (4)
118.6 (4)
117.0 (4)
178.3 (4)
177.4 (4)
179.3 (5)
109.5
O8—C7—C8
O7—C7—C8
95.3 (2)
95.05 (14)
94.95 (18)
177.01 (18)
95.8 (2)
O4—C4—Os2
O1—C1—Os1
O5—C5—Os2
C7—C8—H8A
C7—C8—H8B
C7—C8—H8C
H8A—C8—H8B
H8A—C8—H8C
H8B—C8—H8C
O9—C9—C10
O10—C9—O9
O10—C9—C10
O2—C2—Os1
O3—C3—Os1
O6—C6—Os2
C9—C10—H10A
C9—C10—H10B
C9—C10—H10C
H10A—C10—H10B
H10A—C10—H10C
H10B—C10—H10C
166.67 (14)
87.81 (17)
86.47 (17)
83.26 (8)
82.12 (8)
84.12 (13)
92.53 (14)
175.04 (16)
92.72 (16)
90.8 (2)
109.5
109.5
109.5
109.5
109.5
117.8 (4)
124.8 (4)
117.4 (4)
178.7 (4)
178.3 (5)
178.2 (5)
109.5
109.5
109.5
109.5
109.5
94.9 (2)
95.71 (14)
92.21 (16)
175.92 (16)
94.1 (2)
167.58 (15)
88.79 (17)
109.5
Acta Cryst. (2019). C75
sup-14

supporting information
2
3
Bis(µ-acetato-1κO:2κO′)pentacarbonyl-1κ C,2κ C-[tris(4-methylphenyl)phosphane-1κP]diosmium(Os—Os) (3)
Crystal data
[
M
Os
= 942.88
Triclinic, P1
2
(C
2
H
3
O
2
)
2
(C21
H
21P)(CO)
5
]
Z = 2
F(000) = 892
D = 2.062 Mg m
x
r
−3
a = 10.452 (4) Å
b = 11.229 (4) Å
c = 13.045 (5) Å
α = 82.813 (6)°
β = 89.157 (8)°
γ = 89.457 (9)°
V = 1518.8 (10) Å
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 4436 reflections
θ = 1.8–27.5°
µ = 8.46 mm
T = 100 K
−1
Prism, colorless
0.27 × 0.14 × 0.12 mm
3
Data collection
Rigaku SCX-Mini Mercury 2+ CCD
diffractometer
6915 independent reflections
6534 reflections with I > 2σ(I)
Radiation source: sealed tube
ω–scans
R
int = 0.032
θ
max = 27.4°, θmin = 3.0°
Absorption correction: multi-scan
h = −13→13
k = −14→14
l = −16→16
(ABSCOR; Higashi, 2001)
T
min = 0.605, Tmax = 1.00
3
2350 measured reflections
Refinement
2
Refinement on F
H-atom parameters constrained
2
2
2
Least-squares matrix: full
R[F > 2σ(F )] = 0.020
w = 1/[σ (F
where P = (F
o
) + (0.013P) + 4.878P]
2
2
2
2
o
+ 2F )/3
c
2
wR(F ) = 0.045
(Δ/σ)max = 0.003
Δρmax = 2.80 e Å
Δρmin = −1.05 e Å
−
3
S = 1.02
−
3
6915 reflections
385 parameters
0 restraints
Extinction correction: SHELXL2013
(Sheldrick, 2015a),
*
2
3
-1/4
Hydrogen site location: inferred from
neighbouring sites
Fc =kFc[1+0.001xFc λ /sin(2θ)]
Extinction coefficient: 0.00017 (6)
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
C1
C2
H2
C3
H3
C4
C5
H5
0.1347 (3)
0.0634 (3)
0.0367
0.0318 (3)
−0.0176
0.0714 (3)
0.1440 (3)
0.1730
0.4868 (3)
0.4462 (3)
0.5015
0.3263 (3)
0.3007
0.2420 (3)
0.2823 (3)
0.2264
0.1894 (2)
0.2789 (2)
0.3245
0.3013 (2)
0.3616
0.2368 (3)
0.1486 (3)
0.1042
0.0127 (6)
0.0145 (6)
0.017*
0.0157 (6)
0.019*
0.0151 (6)
0.0168 (6)
0.020*
Acta Cryst. (2019). C75
sup-15

supporting information
C6
H6
0.1744 (3)
0.2229
0.4033 (3)
0.4290
0.1250 (2)
0.0642
0.0143 (6)
0.017*
C7
0.0330 (4)
0.0324
0.0944
0.1124 (3)
0.0893
0.0618
0.2607 (3)
0.3356
0.2281
0.0238 (8)
0.036*
0.036*
H7A
H7B
H7C
C8
C9
H9
−0.0527
0.1019
0.2338
0.036*
0.2576 (3)
0.3909 (3)
0.4338
0.6603 (3)
0.6544 (4)
0.6500
0.0404 (2)
0.0417 (3)
0.1058
0.0125 (6)
0.0263 (8)
0.032*
C10
H10
C11
0.4618 (3)
0.5525
0.4039 (3)
0.2701 (3)
0.2274
0.1983 (3)
0.1076
0.4829 (3)
0.5249
0.6549 (4)
0.6521
0.6592 (3)
0.6658 (3)
0.6704
0.6658 (3)
0.6697
0.6576 (3)
0.7353
−0.0489 (3)
−0.0456
−0.1441 (2)
−0.1455 (3)
−0.2097
−0.0549 (3)
−0.0581
−0.2416 (3)
−0.2590
−0.2983
−0.2308
0.1292 (2)
0.1045 (3)
0.0968
0.0909 (3)
0.0735
0.1024 (2)
0.1246 (3)
0.1312
0.1374 (3)
0.1518
0.0937 (3)
0.0414
0.0275 (8)
0.033*
0.0159 (6)
0.0209 (7)
0.025*
0.0198 (7)
0.024*
0.0215 (7)
0.032*
C12
H12
C13
H13
C14
H14A
H14B
H14C
C15
C16
H16
C17
H17
C18
C19
H19
C20
H20
C21
H21A
H21B
H21C
C22
C23
C24
C25
H25A
H25B
H25C
C26
C27
H27A
H27B
H27C
C28
C29
0.4273
0.5480
0.6424
0.5940
0.032*
0.032*
0.0115 (3)
0.0042 (3)
0.0806
−0.1134 (3)
−0.1160
−0.2277 (3)
−0.2203 (3)
−0.2969
−0.1024 (3)
−0.0997
0.7157 (3)
0.8404 (3)
0.8861
0.8983 (3)
0.9830
0.8350 (3)
0.7104 (3)
0.6650
0.6512 (3)
0.5661
0.0123 (6)
0.0173 (7)
0.021*
0.0186 (7)
0.022*
0.0180 (7)
0.0182 (7)
0.022*
0.0168 (7)
0.020*
−0.3553 (3)
−0.4068
−0.3415
0.8995 (4)
0.8674
0.9855
0.0271 (8)
0.041*
0.041*
0.0734
0.1606
−0.4003
0.8874
0.041*
0.4281 (3)
0.3029 (3)
0.2352 (3)
0.2099 (3)
0.1252
0.2127
0.2753
0.0355 (3)
−0.1052 (3)
−0.1508
0.6810 (3)
0.8760 (3)
0.5818 (3)
0.4613 (3)
0.4330
0.4693
0.4034
0.8338 (3)
0.8548 (3)
0.8404
0.2888 (2)
0.2091 (3)
0.5051 (3)
0.5673 (3)
0.5505
0.6412
0.5505
0.4138 (2)
0.4291 (3)
0.3667
0.0152 (6)
0.0162 (6)
0.0148 (6)
0.0219 (7)
0.033*
0.033*
0.033*
0.0113 (6)
0.0161 (6)
0.024*
−0.1198
−0.1368
0.3296 (3)
0.4871 (3)
0.9379
0.7999
0.9928 (3)
0.8127 (3)
0.4423
0.4881
0.4006 (3)
0.4656 (3)
0.024*
0.024*
0.0169 (7)
0.0198 (7)
Acta Cryst. (2019). C75
sup-16

supporting information
C30
O1
O2
O3
O4
O5
O6
O7
O8
O9
Os1
Os2
P1
0.3235 (3)
0.5308 (2)
0.3279 (2)
0.2162 (2)
0.2747 (2)
0.0720 (2)
0.1085 (2)
0.3398 (3)
0.5950 (2)
0.3396 (3)
0.26266 (2)
0.31080 (2)
0.16761 (7)
0.9004 (3)
0.6419 (2)
0.9606 (2)
0.5898 (2)
0.6648 (2)
0.7938 (2)
0.8585 (2)
1.0848 (2)
0.7955 (3)
0.9413 (2)
0.74048 (2)
0.84058 (2)
0.64666 (7)
0.6145 (3)
0.28700 (19)
0.1523 (2)
0.40969 (17)
0.55293 (18)
0.33261 (17)
0.48501 (17)
0.3535 (2)
0.4569 (2)
0.6878 (2)
0.30025 (2)
0.47863 (2)
0.16222 (6)
0.0176 (7)
0.0244 (6)
0.0252 (6)
0.0177 (5)
0.0173 (5)
0.0159 (5)
0.0141 (4)
0.0280 (6)
0.0335 (7)
0.0300 (6)
0.01069 (4)
0.01191 (4)
0.01095 (15)
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
C1
C2
C3
C4
C5
C6
C7
C8
0.0122 (14)
0.0146 (15)
0.0140 (15)
0.0150 (15)
0.0182 (16)
0.0133 (14)
0.0291 (19)
0.0136 (14)
0.0159 (17)
0.0116 (16)
0.0187 (16)
0.0182 (16)
0.0139 (15)
0.0198 (17)
0.0113 (14)
0.0161 (15)
0.0229 (17)
0.0151 (15)
0.0134 (15)
0.0161 (15)
0.0188 (17)
0.0166 (16)
0.0130 (15)
0.0105 (14)
0.0248 (18)
0.0126 (14)
0.0107 (14)
0.0143 (15)
0.0188 (17)
0.0168 (16)
0.0170 (12)
0.0121 (15)
0.0164 (16)
0.0195 (16)
0.0132 (15)
0.0178 (16)
0.0185 (16)
0.0160 (17)
0.0121 (14)
0.051 (2)
0.0139 (15)
0.0001 (11)
−0.0008 (12)
−0.0031 (12)
−0.0012 (12)
−0.0001 (13)
0.0002 (12)
−0.0043 (14)
−0.0018 (11)
0.0006 (16)
0.0007 (16)
−0.0004 (12)
−0.0011 (14)
−0.0017 (14)
−0.0015 (14)
−0.0002 (12)
−0.0029 (12)
0.0029 (13)
0.0042 (13)
−0.0011 (13)
−0.0019 (13)
0.0091 (15)
−0.0021 (12)
−0.0014 (12)
0.0047 (12)
−0.0001 (14)
−0.0001 (11)
0.0017 (12)
−0.0022 (12)
−0.0023 (13)
0.0034 (13)
0.0083 (11)
−0.0031 (12)
0.0003 (12)
−0.0002 (12)
−0.0043 (12)
0.0012 (13)
0.0014 (12)
0.0014 (15)
0.0014 (12)
−0.0027 (13)
−0.0013 (13)
0.0014 (12)
−0.0025 (13)
−0.0017 (12)
0.0024 (13)
−0.0003 (11)
−0.0039 (13)
−0.0032 (13)
−0.0001 (12)
0.0012 (12)
0.0003 (12)
−0.0022 (15)
−0.0022 (12)
−0.0008 (12)
−0.0002 (12)
0.0013 (14)
0.0000 (11)
−0.0004 (12)
−0.0020 (12)
−0.0044 (14)
−0.0039 (13)
−0.0028 (10)
−0.0014 (12)
−0.0056 (12)
−0.0005 (12)
−0.0026 (12)
−0.0071 (13)
−0.0019 (12)
−0.0025 (14)
−0.0007 (11)
−0.0080 (16)
−0.0082 (17)
−0.0008 (12)
0.0016 (14)
0.0136 (15)
0.0132 (15)
0.0176 (16)
0.0158 (16)
0.0110 (15)
0.0263 (19)
0.0116 (15)
0.0130 (17)
0.0196 (18)
0.0136 (15)
0.0107 (16)
0.0137 (16)
0.0150 (16)
0.0091 (14)
0.0183 (16)
0.0170 (16)
0.0105 (15)
0.0158 (16)
0.0153 (16)
0.027 (2)
0.0123 (15)
0.0191 (17)
0.0169 (16)
0.0226 (18)
0.0139 (15)
0.0218 (17)
0.0184 (16)
0.0231 (18)
0.0194 (17)
0.0218 (13)
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
O1
0.052 (3)
0.0151 (15)
0.033 (2)
0.0313 (19)
0.0288 (19)
0.0171 (15)
0.0174 (16)
0.0164 (16)
0.0289 (18)
0.0254 (18)
0.0191 (16)
0.035 (2)
0.0174 (16)
0.0172 (16)
0.0169 (16)
0.0175 (17)
0.0067 (13)
0.0164 (16)
0.0186 (17)
0.0204 (17)
0.0174 (16)
0.0357 (15)
−0.0003 (14)
0.0001 (14)
−0.0033 (12)
−0.0011 (13)
−0.0033 (13)
−0.0045 (13)
−0.0026 (13)
−0.0020 (13)
−0.0020 (16)
−0.0043 (12)
−0.0049 (13)
−0.0018 (12)
0.0010 (14)
0.0015 (11)
−0.0046 (13)
−0.0046 (13)
−0.0137 (14)
−0.0048 (13)
−0.0093 (11)
Acta Cryst. (2019). C75
sup-17

supporting information
O2
O3
O4
O5
O6
O7
O8
O9
Os1
Os2
P1
0.0264 (13)
0.0231 (12)
0.0220 (12)
0.0109 (10)
0.0108 (10)
0.0348 (15)
0.0141 (13)
0.0373 (15)
0.00957 (6)
0.01044 (6)
0.0100 (3)
0.0222 (13)
0.0169 (12)
0.0143 (11)
0.0222 (12)
0.0178 (11)
0.0190 (13)
0.0394 (16)
0.0333 (15)
0.01199 (7)
0.01276 (7)
0.0127 (4)
0.0249 (14)
0.0133 (11)
0.0154 (12)
0.0156 (11)
0.0147 (11)
0.0297 (15)
0.0526 (19)
0.0224 (14)
0.01086 (7)
0.01335 (7)
0.0104 (4)
−0.0046 (10)
−0.0057 (9)
0.0015 (9)
0.0009 (9)
0.0008 (9)
−0.0072 (11)
0.0008 (11)
0.0082 (12)
−0.00047 (4)
−0.00026 (4)
−0.0016 (3)
0.0025 (11)
−0.0018 (9)
−0.0033 (9)
−0.0002 (9)
−0.0002 (8)
−0.0022 (12)
−0.0028 (12)
−0.0084 (12)
0.00070 (4)
−0.00131 (5)
0.0017 (3)
0.0052 (11)
−0.0018 (9)
−0.0015 (9)
−0.0064 (9)
−0.0055 (9)
−0.0004 (11)
−0.0274 (14)
−0.0151 (12)
−0.00293 (4)
−0.00473 (5)
−0.0024 (3)
Geometric parameters (Å, º)
C1—C6
1.392 (4)
C18—C19
1.395 (5)
C1—C2
C1—P1
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—C7
1.406 (4)
1.820 (3)
1.383 (4)
0.9500
1.398 (5)
0.9500
1.399 (5)
1.507 (5)
1.394 (5)
0.9500
C18—C21
C19—C20
C19—H19
C20—H20
C21—H21A
C21—H21B
C21—H21C
C22—O1
C22—Os1
C23—O2
C23—Os1
C24—O3
1.511 (5)
1.397 (5)
0.9500
0.9500
0.9800
0.9800
0.9800
1.157 (4)
1.858 (3)
1.159 (4)
1.857 (3)
1.256 (4)
1.260 (4)
1.512 (5)
0.9800
0.9800
0.9800
1.255 (4)
1.269 (4)
1.502 (4)
0.9800
C5—C6
C5—H5
C6—H6
0.9500
0.9800
0.9800
0.9800
C7—H7A
C7—H7B
C7—H7C
C8—C13
C8—C9
C8—P1
C9—C10
C9—H9
C10—C11
C10—H10
C11—C12
C11—C14
C12—C13
C12—H12
C13—H13
C14—H14A
C14—H14B
C14—H14C
C15—C20
C15—C16
C15—P1
C16—C17
C24—O4
C24—C25
C25—H25A
C25—H25B
C25—H25C
C26—O5
1.391 (4)
1.394 (5)
1.825 (3)
1.386 (5)
0.9500
1.385 (5)
0.9500
1.400 (5)
1.508 (5)
1.391 (5)
0.9500
0.9500
0.9800
0.9800
0.9800
1.395 (4)
1.399 (4)
1.834 (3)
1.388 (5)
C26—O6
C26—C27
C27—H27A
C27—H27B
C27—H27C
C28—O7
C28—Os2
C29—O8
C29—Os2
C30—O9
C30—Os2
O3—Os1
O4—Os2
O5—Os1
O6—Os2
0.9800
0.9800
1.139 (4)
1.887 (3)
1.148 (4)
1.875 (3)
1.126 (4)
1.979 (3)
2.128 (2)
2.122 (2)
2.127 (2)
2.124 (2)
Acta Cryst. (2019). C75
sup-18

supporting information
C16—H16
C17—C18
C17—H17
0.9500
1.392 (5)
0.9500
Os1—P1
Os1—Os2
2.4261 (10)
2.7624 (8)
C6—C1—C2
C6—C1—P1
C2—C1—P1
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C3—C4—C5
C3—C4—C7
C5—C4—C7
C6—C5—C4
C6—C5—H5
C4—C5—H5
C1—C6—C5
118.4 (3)
123.4 (2)
118.3 (2)
120.6 (3)
119.7
119.7
121.2 (3)
119.4
H21A—C21—H21B
C18—C21—H21C
H21A—C21—H21C
H21B—C21—H21C
O1—C22—Os1
O2—C23—Os1
O3—C24—O4
O3—C24—C25
O4—C24—C25
C24—C25—H25A
C24—C25—H25B
H25A—C25—H25B
C24—C25—H25C
H25A—C25—H25C
H25B—C25—H25C
O5—C26—O6
O5—C26—C27
O6—C26—C27
C26—C27—H27A
C26—C27—H27B
H27A—C27—H27B
C26—C27—H27C
H27A—C27—H27C
H27B—C27—H27C
O7—C28—Os2
O8—C29—Os2
O9—C30—Os2
C24—O3—Os1
C24—O4—Os2
C26—O5—Os1
C26—O6—Os2
C23—Os1—C22
C23—Os1—O5
C22—Os1—O5
C23—Os1—O3
C22—Os1—O3
O5—Os1—O3
109.5
109.5
109.5
109.5
176.5 (3)
179.9 (4)
125.8 (3)
116.7 (3)
117.5 (3)
109.5
119.4
118.1 (3)
120.5 (3)
121.3 (3)
120.8 (3)
119.6
119.6
120.8 (3)
119.6
119.6
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
125.1 (3)
118.1 (3)
116.7 (3)
109.5
109.5
109.5
109.5
109.5
109.5
179.4 (3)
179.5 (3)
173.5 (3)
125.3 (2)
122.6 (2)
125.1 (2)
123.45 (19)
90.83 (14)
96.20 (12)
172.36 (12)
177.66 (12)
89.97 (12)
82.89 (9)
90.97 (11)
98.03 (10)
84.88 (7)
91.10 (7)
96.20 (10)
94.14 (10)
82.15 (6)
C1—C6—H6
C5—C6—H6
C4—C7—H7A
C4—C7—H7B
H7A—C7—H7B
C4—C7—H7C
H7A—C7—H7C
H7B—C7—H7C
C13—C8—C9
C13—C8—P1
C9—C8—P1
109.5
109.5
109.5
117.8 (3)
122.5 (2)
119.5 (2)
121.0 (3)
119.5
119.5
121.8 (3)
119.1
C10—C9—C8
C10—C9—H9
C8—C9—H9
C11—C10—C9
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—C14
C12—C11—C14
C13—C12—C11
C13—C12—H12
C11—C12—H12
C12—C13—C8
C12—C13—H13
C8—C13—H13
C11—C14—H14A
C11—C14—H14B
119.1
117.2 (3)
120.8 (3)
122.0 (3)
121.4 (3)
119.3
119.3
120.9 (3)
119.6
C23—Os1—P1
C22—Os1—P1
O5—Os1—P1
O3—Os1—P1
C23—Os1—Os2
C22—Os1—Os2
O5—Os1—Os2
119.6
109.5
109.5
Acta Cryst. (2019). C75
sup-19

supporting information
H14A—C14—H14B
C11—C14—H14C
H14A—C14—H14C
H14B—C14—H14C
C20—C15—C16
C20—C15—P1
109.5
109.5
109.5
109.5
118.1 (3)
123.0 (2)
118.6 (2)
120.7 (3)
119.6
119.6
121.5 (3)
119.3
O3—Os1—Os2
P1—Os1—Os2
C29—Os2—C28
C29—Os2—C30
C28—Os2—C30
C29—Os2—O4
C28—Os2—O4
C30—Os2—O4
C29—Os2—O6
C28—Os2—O6
C30—Os2—O6
O4—Os2—O6
C29—Os2—Os1
C28—Os2—Os1
C30—Os2—Os1
O4—Os2—Os1
O6—Os2—Os1
C1—P1—C8
81.55 (7)
165.78 (2)
89.92 (15)
94.50 (14)
95.08 (14)
93.53 (13)
173.31 (11)
90.37 (12)
174.59 (11)
92.36 (12)
90.19 (11)
83.72 (9)
C16—C15—P1
C17—C16—C15
C17—C16—H16
C15—C16—H16
C16—C17—C18
C16—C17—H17
C18—C17—H17
C17—C18—C19
C17—C18—C21
C19—C18—C21
C18—C19—C20
C18—C19—H19
C20—C19—H19
C15—C20—C19
C15—C20—H20
C19—C20—H20
C18—C21—H21A
C18—C21—H21B
119.3
91.62 (10)
90.16 (10)
171.95 (10)
84.02 (7)
117.8 (3)
121.0 (3)
121.2 (3)
121.2 (3)
119.4
119.4
120.6 (3)
119.7
83.47 (6)
103.95 (14)
104.43 (14)
104.85 (14)
116.59 (11)
115.81 (11)
109.99 (10)
C1—P1—C15
C8—P1—C15
C1—P1—Os1
C8—P1—Os1
C15—P1—Os1
119.7
109.5
109.5
C6—C1—C2—C3
P1—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C2—C3—C4—C7
C3—C4—C5—C6
C7—C4—C5—C6
C2—C1—C6—C5
P1—C1—C6—C5
C4—C5—C6—C1
C13—C8—C9—C10
P1—C8—C9—C10
C8—C9—C10—C11
C9—C10—C11—C12
C9—C10—C11—C14
C10—C11—C12—C13
C14—C11—C12—C13
C11—C12—C13—C8
C9—C8—C13—C12
P1—C8—C13—C12
C20—C15—C16—C17
P1—C15—C16—C17
C15—C16—C17—C18
−1.1 (5)
177.7 (2)
1.0 (5)
P1—C15—C20—C19
171.4 (2)
0.6 (5)
6.4 (5)
−172.8 (2)
2.3 (4)
−178.5 (2)
6.5 (4)
−173.6 (2)
1.6 (4)
−178.3 (2)
−0.2 (3)
−178.9 (2)
109.5 (3)
−69.2 (3)
−128.9 (2)
52.3 (3)
82.1 (3)
−92.0 (3)
−27.3 (3)
158.6 (3)
−148.7 (2)
37.2 (3)
C18—C19—C20—C15
O4—C24—O3—Os1
C25—C24—O3—Os1
O3—C24—O4—Os2
C25—C24—O4—Os2
O6—C26—O5—Os1
C27—C26—O5—Os1
O5—C26—O6—Os2
C27—C26—O6—Os2
C6—C1—P1—C8
0.0 (5)
−178.3 (3)
−0.9 (5)
177.3 (3)
0.2 (5)
−178.6 (2)
0.8 (5)
0.4 (6)
174.8 (3)
−1.1 (6)
1.4 (6)
−179.0 (4)
−1.2 (5)
179.3 (3)
0.6 (6)
−0.2 (5)
−174.4 (3)
1.5 (5)
−172.3 (3)
0.7 (5)
C2—C1—P1—C8
C6—C1—P1—C15
C2—C1—P1—C15
C6—C1—P1—Os1
C2—C1—P1—Os1
C13—C8—P1—C1
C9—C8—P1—C1
C13—C8—P1—C15
C9—C8—P1—C15
C13—C8—P1—Os1
C9—C8—P1—Os1
C20—C15—P1—C1
6.1 (3)
Acta Cryst. (2019). C75
sup-20

supporting information
C16—C17—C18—C19
C16—C17—C18—C21
C17—C18—C19—C20
C21—C18—C19—C20
C16—C15—C20—C19
−2.2 (5)
176.4 (3)
1.5 (5)
−177.0 (3)
−2.2 (5)
C16—C15—P1—C1
C20—C15—P1—C8
C16—C15—P1—C8
C20—C15—P1—Os1
C16—C15—P1—Os1
179.7 (3)
115.2 (3)
−71.3 (3)
−119.7 (3)
53.8 (3)
Bis(µ-acetato-1κO:2κO′)bis[tris(4-methylphenyl)phosphane]-1κP,2κP-bis(dicarbonylosmium)(Os—Os) p-xylene
sesquisolvate (4@1.5C8H10)
Crystal data
[
M
Os
= 1378.46
Triclinic, P1
2
(C
2
H
3
O
2
2 2 4
) (C21H21P) (CO) ]·1.5C
8
H
10
Z = 2
F(000) = 1362
D = 1.658 Mg m
x
r
−3
a = 12.81225 (16) Å
b = 14.8455 (2) Å
c = 16.6818 (2) Å
α = 98.1785 (11)°
β = 101.7904 (11)°
γ = 113.3846 (14)°
Cu Kα radiation, λ = 1.54184 Å
Cell parameters from 23482 reflections
θ = 3.7–73.2°
µ = 9.55 mm
T = 293 K
−1
Rectangular plate, clear pale yellow
0.11 × 0.07 × 0.02 mm
3
V = 2761.37 (7) Å
Data collection
Rigaku SuperNova AtlasS2 CCD
diffractometer
Radiation source: micro-focus sealed X-ray
tube, SuperNova (Cu) X-ray Source
Mirror monochromator
Detector resolution: 5.2387 pixels mm
ω scans
Absorption correction: gaussian
Tmin = 0.626, Tmax = 1.000
49090 measured reflections
9768 independent reflections
8691 reflections with I > 2σ(I)
R
int = 0.066
-1
θmax = 66.6°, θmin = 3.4°
h = −15→15
k = −17→17
l = −19→19
(CrysAlis PRO; Rigaku OD, 2017)
Refinement
2
Refinement on F
Hydrogen site location: inferred from
neighbouring sites
Least-squares matrix: full
R[F > 2σ(F )] = 0.027
2
2
H-atom parameters constrained
2
2
2
2
wR(F ) = 0.068
w = 1/[σ (F
o
) + (0.0326P) + 0.5818P]
2
2
S = 1.05
where P = (F
o
+ 2F )/3
c
9768 reflections
678 parameters
0 restraints
(Δ/σ)max = 0.009
Δρmax = 2.09 e Å
Δρmin = −1.11 e Å
−
3
−
3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
Os1
Os2
0.52561 (2)
0.72811 (2)
0.31103 (2)
0.49183 (2)
0.17940 (2)
0.22971 (2)
0.01350 (5)
0.01374 (5)
Acta Cryst. (2019). C75
sup-21