A new polymorph of phenyl-selenium trichloride Bloomfield Hannah R.

Article abstract of DOI:10.1107/S2053229619013019

A second polymorph of phenyl-selenium trichloride, PhSeCl3 or C6H5Cl3Se, is disclosed, which is comprised of asymmetric chlorine-bridged noncovalent dimer units rather than polymeric chains. These dimers are each weakly bound to an adjacent dimer through

Full text of DOI:10.1107/S2053229619013019

research papers
A new polymorph of phenylselenium trichloride
Hannah R. Bloomfield and Jamie S. Ritch*
ISSN 2053-2296
Department of Chemistry, The University of Winnipeg, 515 Portage Avenue, Winnipeg, MB, R3B 2E9, Canada.
*Correspondence e-mail: j.ritch@uwinnipeg.ca
A second polymorph of phenylselenium trichloride, PhSeCl3 or C6H5Cl3Se, is
disclosed, which is comprised of asymmetric chlorine-bridged noncovalent
dimer units rather than polymeric chains. These dimers are each weakly bound
to an adjacent dimer through noncovalent SeÁ Á ÁCl bonding interactions. Phenyl
rings within each dimer are oriented in a syn fashion. Density functional theory
(DFT) calculations reveal that the putative anti isomer is within 5 kJ molÀ1 of
the experimentally observed form. This structure represents the first additional
polymorph discovered for an organoselenium trihalide compound.
Received 31 August 2019
Accepted 20 September 2019
Edited by A. R. Kennedy, University of Strath-
clyde, Scotland
Keywords: selenium compound; polymorph;
phenylselenium trichloride; crystal structure;
chalcogen–halogen interaction.
CCDC reference: 1954913
1. Introduction
Organoselenium compounds are of practical interest for
synthetic transformations such as allylic oxidations and
epoxidations. Due to the mild conditions often required, they
are capable of stereo-, regio- and chemoselective reactivity
(Tiecco, 2000).
Supporting information: this article has
supporting information at journals.iucr.org/c
Phenylselenium trichloride is a pale-yellow hygroscopic
solid (Engman, 1987). The high polarizability of selenium,
paired with its high oxidizability and weaker carbon–selenium
bond (compared to the sulfur analogue), makes the phenyl-
selenium group a more versatile auxiliary group compared to
the sulfur analogue (Wessjohann & Sinks, 1998). It has found
use in the large-scale synthesis of ꢀ-phenylselenyl aldehydes
(Houllemare et al., 1997) and has been reacted with alkenes to
form ꢁ-chloroalkyl selenide dichloride adducts for the synth-
esis of polyfunctional molecules in a stereospecific manner
(Garratt & Schmid, 1974). It also been used as a successful
alternative to PhSeBr3 in the synthesis of selenosulfonates,
showing improved yields (Back et al., 1987).
Organoselenium halides also exhibit unique structural
motifs in the solid state, due to the possibility of various
combinations of chalcogen- and halogen-bonding interactions,
which are subtly influenced by substituent effects and crys-
tallization conditions. While quite a few structures have been
reported for selenium(II) halogen compounds, crystal-
lographic data for selenium(IV) compounds remain rare: 213
entries in the Cambridge Structural Database (Groom et al.,
2016; Version 5.40, with updates 1 and 2) are found for the C—
Se—X fragment, but only ten for the C—SeX3 fragment (X =
F, Cl, Br and I). This dearth of structural information for
# 2019 International Union of Crystallography
Acta Cryst. (2019). C75, 1471–1474
https://doi.org/10.1107/S2053229619013019 1471

research papers
Table 1
Experimental details.
higher-valent organoselenium halides provides an opportunity
for new structural discoveries within this class of compounds.
The sole reported polymorph of PhSeCl3 (Barnes et al.,
2005) exhibits a repeating polymeric motif where each
PhSeCl3 molecule bridges two others via a Cl atom. In this
article, we present a second polymorph of phenylselenium
trichloride featuring a dimeric motif grown under different
crystallization conditions, and examine its structural features.
Crystal data
Chemical formula
Mr
C6H5Cl3Se
262.41
Triclinic, P1
150
8.6245 (3), 9.5342 (4), 11.7229 (5)
78.332 (2), 77.789 (2), 66.341 (2)
Crystal system, space group
Temperature (K)
˚
a, b, c (A)
ꢀ, ꢁ, ꢄ (ꢀ)
3
˚
V (A )
855.50 (6)
4
Mo Kꢀ
5.24
Z
Radiation type
ꢅ (mmÀ1
Crystal size (mm)
)
2. Experimental
0.53 Â 0.52 Â 0.35
2.1. Synthesis and crystallization
Data collection
Diffractometer
Absorption correction
Reactions were conducted under an inert atmosphere of
argon using standard Schlenk techniques. Diethyl ether and
hexanes were dried using a solvent purification system, and
stored in PTFE-stoppered flasks over activated 4 A molecular
sieves. CDCl3 was dried by stirring over calcium hydride, then
distilled, degassed using four freeze–pump–thaw cycles and
Bruker APEXII CCD
Numerical (SADABS; Bruker,
2016)
0.456, 0.747
15455, 4426, 3470
Tmin, Tmax
˚
No. of measured, independent and
observed [I > 2ꢆ(I)] reflections
Rint
0.037
0.676
À1
˚
(sin ꢇ/ꢈ)max (A
)
˚
stored in a PTFE-stoppered flask over activated 4 A mol-
Refinement
ecular sieves. Benzeneseleninic acid was prepared according
to the reported procedure of Syper & Młochowski (1984) and
converted to benzeneseleninic anhydride by heating to 180 ꢀC
under dynamic vacuum for 3 h. The title compound, (I), was
prepared in an attempt to synthesize benzeneseleninyl
chloride [i.e. PhSe(O)Cl] via a reported procedure starting
with benzeneseleninic anhydride (Rosenfeld, 1976).
R[F2 > 2ꢆ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.029, 0.051, 1.05
4426
182
H-atom parameters constrained
H-atom treatment
˚
À3
Áꢉmax, Áꢉmin (e A
)
0.46, À0.57
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SHELXT
(Sheldrick, 2015a), SHELXL (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009).
For the synthesis of phenylselenium trichloride, a 100 ml
Schlenk flask was charged with phenylseleninic anhydride
(1.010 g, 2.80 mmol) and diethyl ether (40 ml). The resulting
suspension was cooled to À78 ꢀC and thionyl chloride (3.7 ml,
50.7 mmol) was added dropwise over a period of 2 min. After
stirring for an additional 10 min, the mixture was allowed to
warm slowly to room temperature and stirred for 2 h, followed
by gentle heating to 35 ꢀC for 80 min. The volatiles were then
removed under vacuum and the crude product was washed
with hexanes (3 Â 20 ml). After drying under vacuum, a pale-
cream-coloured solid was obtained (yield: 1.405 g, 5.35 mmol,
2005) applied to all atoms. No symmetry restrictions were
applied during geometry optimizations. The nature of all
stationary points, and the Gibbs energy corrections, were
obtained by analysis of the vibrational frequencies.
3. Results and discussion
In an attempt to prepare benzeneseleninyl chloride [i.e.
PhSe(O)Cl], we conducted the reaction of benzeneseleninic
anhydride with excess thionyl chloride as described previously
(Rosenfeld, 1976). In our hands, this procedure afforded an
excellent yield of phenylselenium trichloride. It seems possible
that in the previously described work, adventitous moisture
partially hydrolyzed the PhSeCl3 product to PhSe(O)Cl, which
was the isolated species. This procedure therefore represents a
new route to PhSeCl3, which is more commonly prepared by
the chlorination of Ph2Se2 with SO2Cl2 (Engman, 1987). Other
methods are known, including the reaction of benzene-
seleninic acid with thionyl chloride (Stuhr-Hansen et al., 1996).
The structure of the title compound, (I), was confirmed by
X-ray studies of single crystals obtained from CDCl3/hexanes,
where a unique unit cell in the space group P1 was found. The
only previously characterized polymorph of PhSeCl3, also with
space group P1, was obtained by the slow cooling of a diethyl
ether solution of the compound. The presently determined
structure has a slightly larger unit-cell volume (by ca 3%)
compared to the known structure.
1
95%). H NMR (CDCl3): ꢂ 8.27–8.19 (m, 2H), 7.61–7.53 (m,
3H). Crystals suitable for X-ray diffraction were obtained
from a solution of the compound in CDCl3, layered with
hexanes and stored at À20 ꢀC.
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. Carbon-bound H atoms
˚
were placed in calculated positions (C—H = 0.95 A) and
refined according to a riding model, with Uiso(H) = 1.2Ueq(C).
No disorder or solvent molecules were noted in the difference
density map.
2.3. Computational studies
Closed-shell density functional theory (DFT) calculations
were performed using the GAMESS software package
(Schmidt et al., 1993). The dispersion-corrected functional
!B97X-D (Chai & Head-Gordon, 2008) was used, with the
triple-ꢃ quality basis set def2-TZVP (Weigend & Ahlrichs,
The unit cell contains two crystallographically independent
molecules arranged in an asymmetric dimeric fashion (Fig. 1)
via two SeÁ Á ÁCl bridging interactions [SeÁ Á ÁCl = 2.7975 (7) and
ꢁ
1472 Bloomfield and Ritch
A new polymorph of phenylselenium trichloride
Acta Cryst. (2019). C75, 1471–1474

research papers
Figure 1
Displacement ellipsoid plot (non-H atoms are drawn at the 50%
probability level) of the dimeric unit of PhSeCl3.
Figure 2
The packing diagram for PhSeCl3.
˚
2.8070 (7) A]. These distances are well within the sum of the
˚
van der Waals radii of 3.65 A (Bondi, 1964). Within each
monomer, the Se—Cl bond lengths for the bridging Cl atoms
˚
are 2.5648 (7)–2.5900 (6) A, while for the terminal Cl atoms
˚
they are in the range 2.1769 (7)–2.2643 (7) A, which are in
˚
accordance with the sum of the covalent radii of 2.22 A
features a structural motif quite similar to the new PhSeCl3
polymorph, with two syn dimers linked together to give
pseudo-octahedral selenium centres with similar bond lengths
and angles. The chlorinated molecule also crystallizes in the
C2/c space group, but is a cocrystallized mixture of syn- and
anti-configuration dimers, and only one of the Se atoms within
the syn-conformer features an additional SeÁ Á ÁCl contact to
another dimer. This previous study illustrates the effect
aromatic ring substituents can have on the aggregation
between ArSeX3 fragments. The present discovery of an
additional polymorph of PhSeCl3 further illustrates that
changing aggregation is possible by simply varying the crys-
tallization conditions, e.g. solvent choice.
To gain further insight into the energetics of the PhSeCl3
system, DFT calculations were performed on the PhSeCl2(ꢅ-
Cl)2SeCl2Ph dimers. Several dispersion-corrected functionals
(B97-D3, M06-2X, PBE0-D3 and !B97X-D) were tested to
examine how closely they reproduced the experimental
geometry of the dimer (ignoring the long-range SeÁ Á ÁCl
contacts). The M06-2X functional had convergence issues and
(Cordero et al., 2008). The atoms comprising the Se2Cl6 unit
˚
are nearly coplanar (r.m.s. deviation of 0.060 A), and the cis
Cl—Se—Cl angles are in the range 84.06 (2)–94.38 (3)ꢀ. The
two phenyl rings of the dimer adopt a syn configuration and
are close to being parallel, with a mean-plane-to-mean-plane
dihedral angle of 5.5 (1)ꢀ. The centroid-to-centroid distance is
˚
3.6987 (2) A. Given the face-to-face nature of the stacked
aromatic rings, an attractive ꢊ–ꢊ stacking interaction is unli-
kely as this orientation is normally electrostatically repulsive
in nature (Martinez & Iverson, 2012). Taking the formula as
C6H5SeCl3, the unit cell features Z = 4 (Fig. 2).
The known polymorph of PhSeCl3 (Barnes et al., 2005)
exhibits a chain polymer structure through noncovalent
˚
interactions [SeÁ Á ÁCl = 2.616 (5)–2.726 (5) A], giving each
selenium centre a square-pyramidal geometry. The monomers
feature similar metrical parameters to those in the present
polymorph. Phenyl substituents from adjacent chains are
interwoven in a slip-stacked fashion, which could possibly lead
to an attractive quadrupole–quadrupole interaction between
the rings (Martinez & Iverson, 2012). Adjacent monomers
feature ca 70ꢀ angles between the SeCl4 basal planes. By
contrast, in the present structure, these are nearly coplanar
and no polymer chains are observed. Instead, longer SeÁ Á ÁCl
˚
contacts in the range 3.3760 (6)–3.4099 (7) A join two adjacent
dimeric units related by a centre of symmetry, giving each
selenium centre a pseudo-octahedral geometry and forming a
double seco-cubane motif (Fig. 3). These Se4 clusters are
weakly bound to adjacent clusters via type I chlor-
˚
ineÁ Á Áchlorine contacts of ca 3.3 A, forming chains.
Figure 3
Two para-halogenated analogues of PhSeCl3 have been
crystallographically characterized (Barnes et al., 2012). The
fluorinated molecule crystallizes in the C2/c space group and
Secondary bonding interactions in the crystal structure of PhSeCl3.
Atoms marked with a prime symbol are related to the unprimed atoms by
(Àx + 1, Ày + 1, Àz + 1).
ꢁ
Acta Cryst. (2019). C75, 1471–1474
Bloomfield and Ritch
A new polymorph of phenylselenium trichloride 1473

research papers
Barnes, N. A., Godfrey, S. M., Halton, R. T. A. & Pritchard, R. G.
(2005). Dalton Trans. pp. 1759–1761.
both functionals using Grimme’s D3 dispersion correction
yielded symmetrically-bridging Cl atoms. Only the !B97X-D
functional closely reproduced the asymmetric dimer structure.
Bond lengths were closely replicated, though the two bridging
interactions linking each PhSeCl3 monomer were longer than
experimentally observed by ca 7%, and the two phenyl rings
were slightly slipped from a face-to-face orientation. It is
possible that attempting to model a second dimer and the
corresponding long-range contacts would result in a more
accurate geometry reproduction, though it was deemed too
computationally expensive at this level of theory.
When the hypothetical anti isomer was modelled it also
exhibited an asymmetric dimer motif, with a Gibbs energy
only ca 5 kJ molÀ1 higher than the syn isomer. While these
computations are simplified from the solid-state structure,
they illustrate the small energy differences between various
conformers and highlight that other polymorphs, i.e. the anti
isomer of PhSeCl3, may be experimentally accessible under
the right crystallization conditions.
Barnes, N. A., Godfrey, S. M., Ollerenshaw, R. T. A., Khan, R. Z. &
Pritchard, R. G. (2012). Dalton Trans. 41, 14583–14593.
Bondi, A. (1964). J. Phys. Chem. 68, 441–451.
Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS Inc.,
Madison, Wisconsin, USA.
Chai, J.-D. & Head-Gordon, M. (2008). Phys. Chem. Chem. Phys. 10,
6615–6620.
´
Cordero, B., Gomez, V., Platero-Prats, A. E., Reves, M., Echeverrıa,
J., Cremades, E., Barragan, F. & Alvarez, S. (2008). Dalton Trans.
´
´
´
pp. 2832–2838.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. &
Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
Engman, L. (1987). J. Org. Chem. 52, 4086–4094.
Garratt, D. G. & Schmid, G. H. (1974). Can. J. Chem. 52, 3599–3606.
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta
Cryst. B72, 171–179.
Houllemare, D., Ponthieux, S., Outurquin, F. & Paulmier, C. (1997).
Synthesis, 1997, 101–106.
Martinez, C. R. & Iverson, B. L. (2012). Chem. Sci. 3, 2191–2201.
Rosenfeld, M. N. (1976). PhD thesis, Imperial College London, UK.
Schmidt, M. W., Baldridge, K. K., Boatz, J. A., Elbert, S. T., Gordon,
M. S., Jensen, J. H., Koseki, S., Matsunaga, N., Nguyen, K. A., Su, S.,
Windus, T. L., Dupuis, M. & Montgomery, J. A. (1993). J. Comput.
Chem. 14, 1347–1363.
Acknowledgements
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
Stuhr-Hansen, N., Henriksen, L. & Kodra, J. T. (1996). Synth.
Commun. 26, 3345–3350.
Syper, L. & Młochowski, J. (1984). Synthesis, 1984, 747–752.
Tiecco, M. (2000). Organoselenium Chemistry. Topics in Current
Chemistry, Vol. 208, edited by T. Wirth, pp. 7–54. Berlin,
Heidelberg: Springer.
Dr David Herbert (Department of Chemistry, University of
Manitoba) is thanked for access to a single-crystal X-ray
diffractometer. Funding for this research was provided by the
Natural Sciences and Engineering Research Council of
Canada.
References
Weigend, F. & Ahlrichs, R. (2005). Phys. Chem. Chem. Phys. 7, 3297–
3305.
Wessjohann, L. & Sinks, U. (1998). J. Prakt. Chem. 340, 189–203.
Back, T. G., Collins, S. & Krishna, M. V. (1987). Can. J. Chem. 65, 38–
42.
ꢁ
1474 Bloomfield and Ritch
A new polymorph of phenylselenium trichloride
Acta Cryst. (2019). C75, 1471–1474

supporting information
supporting information
Acta Cryst. (2019). C75, 1471-1474 [https://doi.org/10.1107/S2053229619013019]
A new polymorph of phenylselenium trichloride
Hannah R. Bloomfield and Jamie S. Ritch
Computing details
Data collection: APEX3 (Bruker, 2016; cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016;
program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL
(Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for
publication: OLEX2 (Dolomanov et al., 2009).
Phenylselenium trichloride
Crystal data
C6H5Cl3Se
Z = 4
Mr = 262.41
Triclinic, P1
F(000) = 504
Dx = 2.037 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 8248 reflections
θ = 2.6–32.6°
a = 8.6245 (3) Å
b = 9.5342 (4) Å
c = 11.7229 (5) Å
α = 78.332 (2)°
β = 77.789 (2)°
γ = 66.341 (2)°
V = 855.50 (6) Å3
µ = 5.24 mm−1
T = 150 K
Prism, clear colourless
0.53 × 0.52 × 0.35 mm
Data collection
Bruker APEXII CCD
diffractometer
φ and ω scans
4426 independent reflections
3470 reflections with I > 2σ(I)
Rint = 0.037
Absorption correction: numerical
(SADABS; Bruker, 2016)
θmax = 28.7°, θmin = 2.6°
h = −11→11
k = −12→12
l = −15→15
T
min = 0.456, Tmax = 0.747
15455 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.029
wR(F2) = 0.051
S = 1.05
4426 reflections
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0095P)2 + 0.5686P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.46 e Å−3
Δρmin = −0.57 e Å−3
182 parameters
0 restraints
Primary atom site location: dual
Hydrogen site location: inferred from
neighbouring sites
Extinction correction: SHELXL2018
(Sheldrick, 2015b),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.0114 (3)
Acta Cryst. (2019). C75, 1471-1474
sup-1

supporting information
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Se1
Se2
Cl4
Cl1
Cl3
Cl2
Cl5
Cl6
C1
C7
C8
H8
C2
0.46873 (3)
0.33135 (3)
0.23956 (8)
0.57258 (8)
0.37555 (9)
0.67527 (8)
0.15514 (9)
0.44520 (9)
0.3008 (3)
0.1696 (3)
0.0049 (3)
−0.029076
0.1329 (3)
0.100984
0.37174 (3)
0.82730 (3)
0.64558 (7)
0.55087 (8)
0.22740 (8)
0.17097 (8)
1.02879 (8)
0.96373 (8)
0.3840 (3)
0.8222 (3)
0.8412 (3)
0.855370
0.37701 (2)
0.29123 (2)
0.46326 (5)
0.21325 (5)
0.53285 (6)
0.30719 (6)
0.37443 (6)
0.14372 (6)
0.2832 (2)
0.1993 (2)
0.2539 (2)
0.334641
0.01526 (7)
0.01719 (7)
0.02005 (13)
0.02304 (14)
0.02807 (16)
0.02984 (16)
0.03339 (17)
0.03359 (17)
0.0155 (5)
0.0170 (5)
0.0199 (5)
0.024*
0.4140 (3)
0.424952
0.3366 (2)
0.417965
0.0185 (5)
0.022*
H2
C6
H6
0.3511 (3)
0.466331
0.3669 (3)
0.347356
0.1649 (2)
0.129613
0.0213 (5)
0.026*
C9
H9
C4
H4
C3
H3
C12
H12
C10
H10
C5
−0.1095 (3)
−0.223387
0.0613 (3)
−0.021439
0.0130 (3)
−0.102844
0.2236 (3)
0.337873
−0.0587 (3)
−0.138341
0.2290 (3)
0.261162
0.8390 (3)
0.852156
0.4096 (3)
0.418381
0.4276 (3)
0.449365
0.7984 (3)
0.784085
0.8180 (3)
0.818728
0.3791 (3)
0.366247
0.1870 (2)
0.222208
0.1506 (2)
0.104667
0.2690 (2)
0.303758
0.0828 (2)
0.047616
0.0700 (2)
0.024752
0.0991 (2)
0.018056
0.0235 (6)
0.028*
0.0218 (6)
0.026*
0.0215 (6)
0.026*
0.0229 (6)
0.027*
0.0253 (6)
0.030*
0.0248 (6)
0.030*
H5
C11
H11
0.1075 (4)
0.142480
0.7958 (3)
0.778644
0.0183 (2)
−0.061869
0.0281 (6)
0.034*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Se1
Se2
Cl4
Cl1
Cl3
0.01433 (13)
0.01727 (13)
0.0202 (3)
0.0160 (3)
0.0340 (4)
0.01787 (13)
0.01849 (14)
0.0267 (3)
0.0320 (4)
0.0354 (4)
0.01336 (13)
0.01750 (14)
0.0139 (3)
0.0201 (3)
0.0197 (3)
−0.00551 (10)
−0.00836 (11)
−0.0100 (3)
−0.0105 (3)
−0.0209 (3)
−0.00342 (10)
−0.00562 (10)
−0.0013 (2)
0.0004 (2)
−0.00121 (10)
0.00074 (10)
−0.0028 (2)
−0.0012 (3)
0.0092 (3)
−0.0104 (3)
Acta Cryst. (2019). C75, 1471-1474
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supporting information
Cl2
Cl5
Cl6
C1
C7
C8
C2
C6
C9
C4
0.0234 (3)
0.0405 (4)
0.0313 (4)
0.0184 (12)
0.0180 (12)
0.0166 (12)
0.0199 (13)
0.0192 (13)
0.0156 (13)
0.0279 (15)
0.0182 (13)
0.0192 (13)
0.0280 (14)
0.0301 (15)
0.0339 (16)
0.0235 (3)
0.0216 (3)
0.0375 (4)
0.0160 (12)
0.0139 (12)
0.0199 (13)
0.0221 (13)
0.0285 (14)
0.0227 (14)
0.0236 (14)
0.0258 (14)
0.0277 (14)
0.0209 (14)
0.0333 (16)
0.0312 (16)
0.0337 (4)
0.0387 (4)
0.0365 (4)
0.0148 (12)
0.0189 (13)
0.0199 (13)
0.0132 (12)
0.0160 (13)
0.0313 (15)
0.0198 (13)
0.0223 (14)
0.0203 (13)
0.0310 (15)
0.0150 (13)
0.0195 (14)
0.0028 (3)
−0.0049 (3)
−0.0105 (3)
−0.0116 (3)
−0.0057 (10)
−0.0083 (10)
−0.0034 (10)
−0.0009 (10)
0.0012 (10)
−0.0084 (11)
−0.0111 (11)
−0.0036 (11)
−0.0022 (11)
−0.0154 (12)
−0.0019 (11)
−0.0074 (12)
−0.0083 (3)
−0.0118 (3)
0.0146 (3)
−0.0062 (3)
−0.0235 (3)
−0.0078 (10)
−0.0043 (10)
−0.0030 (10)
−0.0075 (11)
−0.0094 (11)
−0.0049 (11)
−0.0138 (12)
−0.0105 (11)
−0.0070 (11)
−0.0082 (12)
−0.0154 (13)
−0.0100 (13)
−0.0016 (10)
0.0002 (10)
−0.0028 (11)
−0.0041 (10)
−0.0056 (11)
−0.0011 (12)
0.0012 (11)
−0.0018 (11)
−0.0046 (11)
−0.0026 (12)
−0.0062 (11)
−0.0052 (12)
C3
C12
C10
C5
C11
Geometric parameters (Å, º)
Se1—Cl4i
Se1—Cl4
Se1—Cl1
Se1—Cl3
Se1—Cl2
Se1—C1
Se2—Cl4
Se2—Cl1
Se2—Cl3i
Se2—Cl5
Se2—Cl6
Se2—C7
C1—C2
3.3760 (6)
C8—C9
C2—H2
C2—C3
C6—H6
C6—C5
C9—H9
C9—C10
C4—H4
C4—C3
1.393 (3)
0.9500
1.382 (3)
0.9500
1.388 (3)
0.9500
1.378 (4)
0.9500
1.388 (3)
1.380 (4)
0.9500
0.9500
1.387 (3)
0.9500
2.7975 (7)
2.5648 (7)
2.2643 (7)
2.1881 (7)
1.951 (2)
2.5900 (6)
2.8070 (7)
3.4099 (7)
2.1769 (7)
2.2458 (7)
1.955 (2)
1.389 (3)
1.385 (3)
1.384 (3)
1.380 (3)
0.9500
C4—C5
C3—H3
C12—H12
C12—C11
C10—H10
C10—C11
C5—H5
C11—H11
C1—C6
C7—C8
C7—C12
C8—H8
1.381 (4)
0.9500
0.9500
Cl4—Se1—Cl4i
Cl1—Se1—Cl4
Cl1—Se1—Cl4i
Cl3—Se1—Cl4i
Cl3—Se1—Cl4
Cl3—Se1—Cl1
Cl2—Se1—Cl4i
Cl2—Se1—Cl4
Cl2—Se1—Cl1
Cl2—Se1—Cl3
C1—Se1—Cl4
C1—Se1—Cl4i
90.204 (17)
84.71 (2)
89.433 (18)
87.29 (2)
91.45 (2)
174.95 (2)
83.89 (2)
172.03 (2)
89.87 (3)
93.60 (3)
89.59 (7)
179.21 (7)
C6—C1—C2
C8—C7—Se2
C12—C7—Se2
C12—C7—C8
C7—C8—H8
C7—C8—C9
C9—C8—H8
C1—C2—H2
C3—C2—C1
C3—C2—H2
C1—C6—H6
C1—C6—C5
121.9 (2)
118.66 (18)
119.06 (18)
122.3 (2)
121.0
118.0 (2)
121.0
120.7
118.7 (2)
120.7
120.8
118.4 (2)
Acta Cryst. (2019). C75, 1471-1474
sup-3

supporting information
C1—Se1—Cl1
C1—Se1—Cl3
C1—Se1—Cl2
Cl4—Se2—Cl1
Cl4—Se2—Cl3i
Cl1—Se2—Cl3i
Cl5—Se2—Cl4
Cl5—Se2—Cl1
Cl5—Se2—Cl3i
Cl5—Se2—Cl6
Cl6—Se2—Cl4
Cl6—Se2—Cl1
Cl6—Se2—Cl3i
C7—Se2—Cl4
C7—Se2—Cl1
C7—Se2—Cl3i
C7—Se2—Cl5
C7—Se2—Cl6
Se2—Cl4—Se1
Se1—Cl1—Se2
C2—C1—Se1
C6—C1—Se1
89.78 (7)
93.48 (7)
96.25 (7)
84.06 (2)
81.751 (18)
83.668 (19)
90.83 (3)
172.41 (3)
90.06 (2)
94.38 (3)
172.72 (3)
90.24 (3)
93.14 (2)
90.64 (7)
89.74 (7)
170.39 (7)
95.94 (7)
93.87 (7)
95.36 (2)
95.70 (2)
118.78 (17)
119.29 (18)
C5—C6—H6
C8—C9—H9
C10—C9—C8
C10—C9—H9
C3—C4—H4
C5—C4—H4
C5—C4—C3
120.8
119.7
120.5 (2)
119.7
119.8
119.8
120.3 (2)
120.2 (2)
119.9
119.9
120.7
118.6 (2)
120.7
119.8
120.3 (2)
119.8
119.8
120.5 (2)
119.8
119.9
120.3 (2)
119.9
C2—C3—C4
C2—C3—H3
C4—C3—H3
C7—C12—H12
C7—C12—C11
C11—C12—H12
C9—C10—H10
C9—C10—C11
C11—C10—H10
C6—C5—H5
C4—C5—C6
C4—C5—H5
C12—C11—H11
C10—C11—C12
C10—C11—H11
Symmetry code: (i) −x+1, −y+1, −z+1.
Acta Cryst. (2019). C75, 1471-1474
sup-4