A low-temperature polymorph of m-quinquephenyl

Article abstract of DOI:10.1107/S0108270112046392

A low-temperature polymorph of 1,1′:3′,1′′: 3′′,1′′′:3′′′, 1′′′′-quinquephenyl (m-quinquephenyl), C30H22, crystallizes in the space group P21/c with two molecules in the asymmetric unit. The crystal is a three-component nonmerohedral twin. A previously reported room-temperature polymorph [Rabideau, Sygula, Dhar & Fronczek (1993). Chem. Commun. pp. 1795-1797] also crystallizes with two molecules in the asymmetric unit in the space group P . The unit-cell volume for the low-temperature polymorph is 4120.5(4)A³, almost twice that of the room-temperature polymorph which is 2102.3(6)A³. The molecules in both structures adopt a U-shaped conformation with similar geometric parameters. The structural packing is similar in both compounds, with the molecules lying in layers which stack perpendicular to the longest unit-cell axis. The molecules pack alternately in the layers and in the stacked columns. In both polymorphs, the only interactions between the molecules which can stabilize the packing are very weak C-H...π interactions.

Full text of DOI:10.1107/S0108270112046392

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
and enthalpies of vaporization, m-quinquephenyl, (I), has
been synthesized, following a similar procedure to that used
for a previously optimized Suzuki–Miyaura cross-coupling
reaction (Suzuki, 2011; Miyaura, 2002) for polyphenyl com-
pounds (Lima et al., 2011). A search of the literature revealed
that (I) had already been structurally characterized by X-ray
diffraction at room temperature (283–303 K; Rabideau et al.,
ISSN 0108-2701
A low-temperature polymorph of
1993). Nevertheless, it is well known that isomers belonging to
m-quinquephenyl
the parent series of p-polyphenyl oligomers [n(phenyl) = 3–4]
undergo solid-phase transitions (Baker et al., 1990, and
references therein). Those transitions are characterized by an
order/disorder phase change, from twisted (at lower
temperatures) to planar (when heated) (Delugeard et al., 1976;
Baudour et al., 1978), so the question of whether a phase
transition would occur in the m-quinquephenyl isomer was
raised, driving interest in the structural characterization of the
compound at low temperatures. Furthermore, the identifica-
tion and characterization of the polymorphic forms is essential
to an accurate interpretation of, for instance, experimental
calorimetric results.
a
b
b
Ligia R. Gomes, R. Alan Howie, John Nicolson Low, *
c
c
Ana S. M. C. Rodrigues and Lu ´ı s M. N. B. F. Santos
a
REQUIMTE, Departamento de Qu ´ı mica e Bioqu ´ı mica, Faculdade de Ci eˆ ncias,
Universidade do Porto, Rua do Campo Alegre 687, P-4169 007 Porto, Portugal,
b
Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen
c
AB24 3UE, Scotland, and Centro de Investiga ¸c ˜a o em Qu ´ı mica, Departamento de
Qu ´ı mica e Bioqu ´ı mica, Faculdade de Ci eˆ ncias, Universidade do Porto, Rua do
Campo Alegre 687, P-4169 007 Porto, Portugal
Correspondence e-mail: jnlow111@gmail.com
Received 31 October 2012
Accepted 9 November 2012
Online 13 November 2012
0
0
00 00 000 000 0000
A low-temperature polymorph of 1,1 :3 ,1 :3 ,1 :3 ,1 -
quinquephenyl (m-quinquephenyl), C H , crystallizes in
30
22
the space group P2 /c with two molecules in the asymmetric
1
unit. The crystal is a three-component nonmerohedral twin. A
previously reported room-temperature polymorph [Rabideau,
Sygula, Dhar & Fronczek (1993). Chem. Commun. pp. 1795–
1797] also crystallizes with two molecules in the asymmetric
unit in the space group P1. The unit-cell volume for the low-
3
temperature polymorph is 4120.5 (4) A , almost twice that of
˚
3
the room-temperature polymorph which is 2102.3 (6) A . The
˚
The low-temperature (LT) measurement, performed at
50 K, revealed that (I) crystallizes in the space group P2 /c
molecules in both structures adopt a U-shaped conformation
with similar geometric parameters. The structural packing is
similar in both compounds, with the molecules lying in layers
which stack perpendicular to the longest unit-cell axis. The
molecules pack alternately in the layers and in the stacked
columns. In both polymorphs, the only interactions between
the molecules which can stabilize the packing are very weak
C—Hꢀ ꢀ ꢀꢀ interactions.
1
1
3
˚
with a unit-cell volume of 4120.5 (4) A , and with two mol-
ecules (LTA and LTB) in the asymmetric unit (Fig. 1). These
data show that the structure at low temperature is a poly-
morph of the earlier structure of (I) found by Rabideau et al.
(1993) in a room-temperature (RT) determination (R = 0.052).
At RT, (I) crystallizes in the space group P1 with a unit-cell
3
volume of 2102.3 (6) A , and with two molecules in the
˚
asymmetric unit (RTA and RTB; Fig. 2). The RT unit-cell
dimensions are: a = 7.7620 (6), b = 13.618 (2) and c =
Comment
˚
2
1.623 (5) A, and ꢁ = 80.58 (2), ꢂ = 85.26 (1) and ꢃ =
ꢁ
Polyphenyls are used in technological industries, either
directly (e.g. as dyes, thermal printing materials or coolants) or
as starting materials for functionalized derivatives that are
incorporated in, for instance, nonspreading lubricants, emul-
sifiers, optical brighteners, crop protection products and
plastics. In spite of this, experimental data for the thermo-
chemical parameters of these compounds that would permit
inferences to be made concerning not only their relative
stability, but also structure/molecular energetics relationships
or thermophysical properties, are scarce.
89.71 (1) . As can be seen from the crystal data table for the
LT structure, there is a rough relationship between the unit-
0
0
cell dimensions for each compound: a (RT) ’ b(LT), b ’ a,
0
0
ꢁ
0
0
ꢁ
c ’ c/2, ꢁ ’ (180 ꢂ ꢂ) , and ꢂ and ꢃ are quite close to 90 , so
swapping the a and b axes and doubling c effectively changes
the RT cell to the LT cell.
The m-polyphenyls might be expected to adopt a zigzag
conformation in order to minimize steric repulsion between
the phenyl groups, but in both the LTand RT crystal structures
of (I) the U-shaped conformation is preferred. Theoretical
calculations made earlier using MM2/87 (Rabideau et al.,
1993) showed that there is no apparent energetic restraint
preventing the zigzag conformation in favour of the U-shaped
In the course of a thermochemical study of polyphenylenes,
particularly with regard to the effect of isomerization on the
fusion temperatures, heat capacities, enthalpies of formation
o492 # 2012 International Union of Crystallography
doi:10.1107/S0108270112046392
Acta Cryst. (2012). C68, o492–o497

organic compounds
Figure 2
Molecules (a) RTAand (b) RTBof (I), taken from Rabideau et al. (1993),
showing the atom-numbering scheme. The spheres are of arbitrary size.
Figure 1
Molecules (a) LTA and (b) LTB of (I), showing the atom-numbering
scheme. Displacement ellipsoids are drawn at the 30% probability level.
given in columns 4 and 6 of Table 2. The r.m.s. bond-length and
bond-angle differences between equivalent bonds and angles
within each pair of molecules are also given in Table 2. As a
consequence of the arbitrary choice of asymmetric unit, mol-
ecules A and B are mirror images of one another, as shown by
the need to invert one of them to optimize the fit with the
other. The MOLFIT parameters and the dihedral angles are
indicative that the molecules have very similar conformations,
as can be best viewed in the plots of the fitted molecules given
in Fig. 3.
conformation. The calculations were indicative that both
conformers and their intermediate geometries are energeti-
cally similar, with torsion barriers of about 5 kJ mol . All
molecules have a very similar geometry. The dihedral angles
between successive rings along the chain (Table 1) show that
they lie within the same angular range and show similar trends.
The results of a least-squares fit of the 30 C atoms using
PLATON MOLFITwith quaternion transformation (Mackay,
ꢂ1
1984; Spek, 2009) for the molecules in pairs are given in
Table 2. Columns 3 and 5 provide values for the root-mean-
square (r.m.s.) distance between equivalent (overlapping/
superimposed) atoms in the fitted molecules. These give rise to
The values in Table 3 are consistent with the molecules in
each bimolecular asymmetric unit being related to one
another by a noncrystallographic glide plane, which ensures
the invariance of the z coordinates for each pair of molecules;
for the RT structure it is an a-glide parallel to (010), while for
values for the molecular isometricity index, defined as I (n*) =
i
2
1/2
|
[Æ(ÁR ) /n] ꢂ 1| ꢃ 100 for n = 30 (K a´ lm a´ n et al., 1993),
i
ꢄ
Acta Cryst. (2012). C68, o492–o497
Gomes et al.
30
C H22 o493

organic compounds
Figure 5
A view of the packing of the molecules in the unit cell of the RT form of
(
I), viewed along the b axis. H atoms have been omitted for clarity.
Molecules labelled with an asterisk (*) are at the symmetry position
ꢂx + 1, ꢂy + 1, ꢂz + 1).
(
another, with a fractional separation of 0.5 along the b or a
axis and an offset of 0.25 along the a or b axis for the LT and
RT structures, respectively. As shown in Figs. 4 and 5, the unit
cell of the RT structure contains two layers of molecules
1
3
centred on z = 4 and 4 and related to one another by the
operation of crystallographic centres of symmetry, which is the
only relationship between neighbouring layers as they are
stacked in the c direction. The situation in the LT structure is
more complex. As shown in Figs. 6 and 7, the unit cell of the
LT structure encompasses four layers of molecules centred on
1
8
3
8
5
8
7
8
1
8
3
z = , , and . The layers at z = and 8 are related to one
another by the operation of crystallographic twofold screw
5
7
axes, and the same is true for the layers at z = and . The
5
8
8
1
layers at z = 8 and 8 are related by the operation of crystal-
lographic c-glide planes and the same is true for the layers at z
3
7
8
1
= 8
and and are related to one another, as they are stacked in the
and . Pairs of layers are now, of course, centred on z =
3
4
Figure 3
4
Molecular overlay diagrams for all six possible combinations of the
molecules of the two structures. Black denotes the RT structure and
lighter shading the LT one.
c direction, by the operation of crystallographic centres of
inversion, together with the operation of the crystallographic
c-glide planes already mentioned.
the LT structure it is a b-glide parallel to (100). Thus, in both
structures, the molecules in the asymmetric unit sit above one
There are no ꢀ–ꢀ interactions in the structures. Table 4
gives details of distances and angles for the most relevant close
contacts between molecules. These values are indicative that
Figure 6
A view of the packing of the molecules in the unit cell of the LT form of
(I), viewed along the b axis. H atoms have been omitted for clarity.
Molecules labelled with an asterisk (*), hash (#), ampersand (&), plus
sign (+) or dollar sign ($) are at the symmetry positions (ꢂx + 1, ꢂy + 1,
Figure 4
A view of the packing of the molecules in the unit cell of the RT form of
(I), viewed along the a axis. H atoms have been omitted for clarity.
Molecules labelled with an asterisk (*) are at the symmetry position
1
2
1
2
3
2
1
2
1
2
1
2
ꢂz + 1), (ꢂx + 1, y + , ꢂz + ), (x, ꢂy + , z + ), (ꢂx + 1, y ꢂ , ꢂz + ) or
1
1
(ꢂx + 1, ꢂy + 1, ꢂz + 1).
(x, ꢂy + , z + ), respectively.
2
2
ꢄ
o494 Gomes et al.
C H
30 22
Acta Cryst. (2012). C68, o492–o497

organic compounds
Figure 7
A view of the packing of the molecules in the unit cell of the LT form of (I), viewed along the a axis. H atoms have been omitted for clarity. Molecules
1
labelled with an asterisk (*), hash (#), ampersand (&), plus sign (+) or dollar sign ($) are at the symmetry positions (ꢂx + 1, ꢂy + 1, ꢂz + 1), (ꢂx + 1, y + ,
2
1
2
3
2
1
2
1
2
1
2
1
2
1
2
ꢂz + ), (x, ꢂy + , z + ), (ꢂx + 1, y ꢂ , ꢂz + ) or (x, ꢂy + , z + ), respectively.
˚
the contacts are too weak and may not be considered as
significant C—Hꢀ ꢀ ꢀꢀ interactions. Comparison of the values
between polymorphs, for corresponding contacts, suggests that
they are stronger in the LT polymorph. The packing motifs,
molecular conformations and mutual orientations of the
molecules are very similar in the two structures. Nevertheless,
the LT polymorph appears to have a more efficient packing
than the RT one, as suggested by the volume allocated per
interactions (Hꢀ ꢀ ꢀCg distances in the range 2.83–2.97 A, with
ꢁ
angles at H of 130–137 ) stabilizing the supramolecular
structure. In the case of the LT form, there are ten potential
˚
C—Hꢀ ꢀ ꢀꢀ interactions (Hꢀ ꢀ ꢀCg distances of 2.69–2.97 A and
ꢁ
angles at H of 126–144 , of which eight have angles at H
ꢁ
greater than 139 ) which stabilize the packing. This is the
converse of the situation for the HT and LT forms of m-
quinquephenyl presented here, where the impact of C—Hꢀ ꢀ ꢀꢀ
interactions on the supramolecular structures is minimal
compared with the p-isomer. Also, apart from the change in
torsion angles for the outer phenyl rings in molecule LTB, the
molecular geometry is virtually unaffected. These differences
may help to understand the effect of isomerization on some of
the physical properties of the polyphenyls, such as melting
points, or enthalpies of formation or vaporization.
3
˚
molecule in the LT structure (approximately 10 A less). This
fact is obviously reflected in macroscopic terms by the slight
differences in the values for the densities, of 1.233 (calculated)
ꢂ3
and 1.209 Mg m (measured) (Rabideau et al., 1993) in the
LT and RT structures, respectively. Roughly speaking, for
organic compounds, the linear thermal expansion coefficient is
ꢂ1
less than 0.0001 K , which would give a density of about
ꢂ3
1.19 Mg m for the LT polymorph at room temperature,
Due to the simplicity of the elemental composition of
polyphenyls, the only possible stabilization mechanism of their
supramolecular structures is through the contribution of weak
C—Hꢀ ꢀ ꢀꢀ and/or ꢀ–ꢀ interactions, thus making them good
models for the study of the impact of these interactions on
molecular geometry, packing or molecular motion constraints,
parameters that will be reflected in their physical properties.
As far as the p-polyphenyls are concerned, the phase change
from low to high temperature leads to a reduction in the
interactions and the molecular motion becomes less
constrained. This may explain the high heat capacity of these
compounds, which makes them good candidates for use as
coolants. The molecular motion, symmetry and higher number
of C—Hꢀ ꢀ ꢀꢀ interactions which the p-oligomers establish in
relation to the m-oligomers may explain the higher melting
points of the former. Despite that, our comparative analysis of
two m-quinquephenyl polymorphs has highlighted the role of
weak close contacts on cell volume and densities.
considering the temperature difference of 140 K between the
measurements. The differences found in the densities may be
attributed mainly to the thermal expansion of the compound,
drawing attention to the role that entropy may play in the
formation of the polymorphs.
This kind of polymorphism contrasts with that shown by the
homologous p-quinquephenyl. The phase transitions in
p-polyphenyls are well established for the case of p-terphenyl
and p-quaterphenyl. Those transitions are accompanied by a
change in the crystal structure (space group P1 before the
transition and space group P2 /n after the phase transition)
1
associated with an energy change (heat of transition), and
therefore a change in the absolute heat capacity of the
compound, at the temperature of transition. The structure of
the parent p-quinquephenyl has not been determined at low
temperatures, but Saito et al. (2000) have suggested, based on
the measurement of heat capacity excess with temperature,
that the parent p-quinquephenyl would have a twist phase
transition at about 264 K, similar to what is observed in the
p-polyphenyls (n = 3, 4). In the case of p-quaterphenyl, on the
basis of the available structural data [p-quaterphenyl at 283–
Experimental
m-Quinquephenyl was synthesized using the Suzuki–Miyaura aryl
cross-coupling method by adapting the procedure described in the
literature (Miyaura & Suzuki, 1995; Liu et al., 2006). The compound
was synthesized by the reaction of a mixture of 1,3-dibromobenzene
303 K (R = 0.045; Delugeard et al., 1976) and p-quaterphenyl
at 110 K (R = 0.104; Baudour et al., 1978)], it appears that the
individual molecules have significantly different conforma-
tions in the high-temperature phase (virtually planar and
centrosymmetric) and low-temperature phase (nonplanar and
noncentrosymmetric). Furthermore, they each have entirely
different supramolecular structures. In the case of the HT
form, there are four potential but very weak C—Hꢀ ꢀ ꢀꢀ
(3 mmol), 3-boronic acid (11 mmol), Pd(OAc)
2
(0.1 mmol) and
K
CO (15 mmol) in distilled water (15 ml), toluene (30 ml) and
2 3
ethanol (10 ml). The mixture was stirred under a nitrogen atmos-
phere for approximately 10 h at 350 K. The product was purified by
recrystallization from methanol and by sublimation under reduced
pressure (<10 Pa). The purity of the compound was checked by gas
ꢄ
Acta Cryst. (2012). C68, o492–o497
Gomes et al.
30
C H22 o495

organic compounds
Table 1
Dihedral angles ( ) between adjacent planes.
Table 3
Coordinates of the centroids of the molecules in the asymmetric units of
the LT and RT forms of (I).
ꢁ
The angles are measured from the ring containing atom C11 (ring 1) through
to that containing C51 (ring 5) in all molecules.
Molecule
x
y
z
Áx
Áy
Áz
Rings
LTA
LTB
RTA
RTB
LTA
LTB
RTA
RTB
0.6876
0.9459
0.3231
0.8220
0.7492
0.2502
0.1872
0.4447
0.1196
0.1187
0.2602
0.2655
0.2583
0.4989
0.4990
0.2575
0.0009
0.0053
1–2
2–3
3–4
4–5
36.28 (11)
32.11 (11)
31.54 (11)
34.16 (12)
35.30 (12)
33.91 (11)
30.89 (12)
37.07 (13)
36.25 (9)
32.22 (8)
30.67 (8)
35.68 (10)
36.11 (9)
34.39 (8)
30.51 (9)
35.68 (10)
domains. The TwinRotMat option was used to generate the HKLF 5
reflection file from the original data, which had been integrated
initially as a nontwinned data set.
chromatography, using an HP 4890 apparatus equipped with an HP-5
column [crosslinked, 5% diphenyl and 95% dimethylpolysiloxane,
showing a % (m/m) purity greater than 99.8%]. The relative atomic
masses used were those recommended by the IUPAC Commission in
The 202, 202, 200, 200, 204 and 102 reflections were omitted as they
were obscured by the beam stop.
2007 (Wieser & Berglund, 2009). Crystals suitable for X-ray diffrac-
tion were obtained by recrystallization by evaporation from a solu-
tion in methanol–acetone (3:1 v/v).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2
and SAINT (Bruker, 2004); data reduction: SAINT; program(s) used
to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to
refine structure: SHELXL97 (Sheldrick, 2008) and OSCAIL
(McArdle et al., 2004); molecular graphics: PLATON (Spek, 2009);
software used to prepare material for publication: SHELXL97.
Crystal data
˚
V = 4120.5 (4) A
3
C
30
H
22
M
r
= 382.48
Z = 8
Mo Kꢁ radiation
ꢄ = 0.07 mm
T = 150 K
Monoclinic, P2 =c
˚
a = 13.5740 (7) A
b = 7.1809 (4) A
˚
c = 42.833 (2) A
ˆ
1
The authors are grateful to the Funda c¸ a˜ o para a Ciencia e
Tecnologia (FCT), Lisbon, Portugal, and to FEDER for
financial support to the Centro de Investiga c¸ a˜ o em Qu ı´ mica,
University of Porto. ASMCR acknowledges financial support
from FCT and the European Social Fund (ESF) under the
Community Support Framework (CSF) for the award of PhD
Research Grant No. SFRH/BD/81261/2011.
ꢂ1
˚
0.30 ꢃ 0.08 ꢃ 0.02 mm
ꢁ
ꢂ = 99.274 (4)
Data collection
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
28626 measured reflections
8455 independent reflections
6424 reflections with I > 2ꢅ(I)
(
T
SADABS; Bruker, 2004)
min = 0.979, Tmax = 0.999
Rint = 0.042
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: LN3153). Services for accessing these data are
described at the back of the journal.
Refinement
2
2
R[F > 2ꢅ(F )] = 0.049
wR(F ) = 0.155
543 parameters
H-atom parameters constrained
2
References
˚
ꢂ3
Áꢆmax = 0.22 e A
S = 1.02
8453 reflections
Baker, K. N., Fratini, A. V. & Adams, W. W. (1990). Polymer, 31, 1623–1631.
Baudour, J.-L., D e´ lugeard, Y. & Rivet, P. (1978). Acta Cryst. B34, 625–628.
Bruker (2004). APEX, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Áꢆmin = ꢂ0.27 e A˚
ꢂ3
˚
H atoms were treated as riding, with aromatic C—H = 0.95 A and
Delugeard, Y., Desuche, J. & Baudour, J. L. (1976). Acta Cryst. B32, 702–705.
K a´ lm a´ n, A., P a´ rk a´ nyi, L. & Argay, G. (1993). Acta Cryst. B49, 1039–1049.
Lima, C. F. R. A. C., Rodriguez-Borges, J. E. & Santos, L. M. N. B. F. (2011).
Tetrahedron, 67, 689–697.
Uiso(H) = 1.2Ueq(C). The positions of the H atoms were calculated
and checked on a difference map during the refinement.
The crystal was a three-component nonmerohedral twin and was
refined using an HKLF 5 reflection file (Sheldrick, 2008) with BASF
values of 0.246 (2) and 0.0491 (3). This was discovered after an initial
attempt at refinement gave a high R factor and the TwinRotMat
option in PLATON (Spek, 2009) revealed the existence of three twin
Liu, L. Y., Zhang, Y. & Xin, B. (2006). J. Org. Chem. 71, 3994–3997.
Mackay, A. L. (1984). Acta Cryst. A40, 165–166.
McArdle, P., Gilligan, K., Cunningham, D., Dark, R. & Mahon, M. (2004).
CrystEngComm, 6, 303–309.
Miyaura, N. (2002). Top. Curr. Chem. 219, 11–59.
Miyaura, A. & Suzuki, A. (1995). Chem. Rev. 95, 2457–2483.
Table 2
MOLFIT parameters for overlays of all combinations of molecules from both polymorphs.
An asterisk (*) denotes an inverted molecule.
Molecule
Molecule
R.m.s. fit
(
Isometricity
weighted) (A) index (weighted) (unit weights) (A) index (unit)
R.m.s. fit
Isometricity
R.m.s. fit of
bond lengths (A) angles ( )
R.m.s. fit of
ꢁ
Fit rotation
ꢁ
˚
˚
˚
angle ( )
LTA*
RTA*
LTA*
LTA
LTB
LTB*
LTB
RTB
RTA
RTB
RTA
RTB
0.044
0.053
0.036
0.063
0.037
0.061
95.6
94.7
96.4
93.7
96.3
93.9
0.038
0.049
0.032
0.060
0.036
0.054
96.2
95.1
96.8
94.0
96.4
94.6
0.0045
0.0042
0.0065
0.0066
0.0072
0.0076
0.297
0.270
0.353
0.332
0.316
0.292
179.68
179.79
89.91
179.69
ꢂ179.72
ꢂ90.58
ꢄ
o496 Gomes et al.
C H
30 22
Acta Cryst. (2012). C68, o492–o497

organic compounds
Table 4
Short contacts (A, ) between molecules.
˚
ꢁ
Cg is the centre of gravity of the ring containing the indicated atom.
Polymorph
C
H
Ring (pivot atom) Symmetry operator for ring C—H
Hꢀ ꢀ ꢀCg
Cꢀ ꢀ ꢀCg
Angle at H
LT
LT
LT
LT
LT
C53B
C25B
C15A
C46A
C46B
H53B
H25B
H15A
H46A
H46B
Cg (C51A)
Cg (C21A)
Cg (C11B)
Cg (C31B)
Cg (C31A)
x, y, z
0.95
0.95
0.95
0.95
0.95
2.96
2.91
3.00
2.95
3.00
3.801 (3)
3.521 (3)
3.451 (3)
3.354 (2)
3.319 (3)
149
123
111
107
101
x + 1, y ꢂ 1, z
x ꢂ 1, y + 1, z
x, y, z
x, y ꢂ 1, z
RT
RT
RT
RT
RT
C53B
C25B
C15A
C46A
C46B
H53B
H25B
H15A
H46A
H46B
Cg (C51A)
Cg (C21A)
Cg (C11B)
Cg (C31B)
Cg (C31A)
x, y ꢂ 1, z
x + 1, y + 1, z
x ꢂ 1, y ꢂ 1, z
x, y, z
0.97
1.03
0.95
1.00
0.99
3.03
2.97
3.12
2.97
3.06
3.867
3.606
3.503
3.404
3.346
145
122
107
107
98
x + 1, y, z
Rabideau, P. W., Sygula, A., Dhar, R. K. & Fronczek, F. (1993). Chem.
Commun. pp. 1795–1797.
Saito, K., Yamamura, Y. & Sorai, M. (2000). Bull. Chem. Soc. Jpn, 73, 2713–
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Suzuki, A. (2011). Angew. Chem. Int. Ed. 50, 6722–6737.
2718.
Wieser, M. E. & Berglund, M. (2009). Pure Appl. Chem. 81, 2131–2156.
ꢄ
Acta Cryst. (2012). C68, o492–o497
Gomes et al.
30
C H22 o497

supplementary materials
supplementary materials
Acta Cryst. (2012). C68, o492–o497 [doi:10.1107/S0108270112046392]
A low-temperature polymorph of m-quinquephenyl
Ligia R. Gomes, R. Alan Howie, John Nicolson Low, Ana S. M. C. Rodrigues and Luís M. N. B. F.
Santos
1
,1′:3′,1′′:3′′,1′′′:3′′′,1′′′′-quinquephenyl
Crystal data
C
M
30
H
22
F(000) = 1616
= 1.233 Mg m
−3
r
= 382.48
D
x
Monoclinic, P2
1
/c
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 28626 reflections
θ = 2.9–26.5°
µ = 0.07 mm
T = 150 K
Hall symbol: -P 2ybc
a = 13.5740 (7) Å
b = 7.1809 (4) Å
c = 42.833 (2) Å
β = 99.274 (4)°
−1
Needle, colourless
0.30 × 0.08 × 0.02 mm
3
V = 4120.5 (4) Å
Z = 8
Data collection
Bruker APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
Detector resolution: 8.33 pixels mm
ω scans
Absorption correction: multi-scan
28626 measured reflections
8455 independent reflections
6424 reflections with I > 2σ(I)
R
int = 0.042
-1
θmax = 26.5°, θmin = 2.9°
h = −17→16
k = −9→9
(
SADABS; Bruker, 2004)
l = −53→15
T
min = 0.979, Tmax = 0.999
Refinement
2
Refinement on F
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
Least-squares matrix: full
R[F > 2σ(F )] = 0.049
2
2
2
wR(F ) = 0.155
S = 1.02
H-atom parameters constrained
2
2
2
8453 reflections
543 parameters
0 restraints
w = 1/[σ (F
where P = (F
o
) + (0.0988P) ]
2
2
o
+ 2F )/3
c
(Δ/σ)max = 0.001
Δρmax = 0.22 e Å
Δρmin = −0.27 e Å
−
3
Primary atom site location: structure-invariant
direct methods
−
3
Acta Cryst. (2012). C68, o492–o497
sup-1

supplementary materials
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
2
2
Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F ,
2
2
2
conventional R-factors R are based on F, with F set to zero for negative F . The threshold expression of F > σ(F ) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F
2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
C11A
C12A
H12A
C13A
H13A
C14A
H14A
C15A
H15A
C16A
H16A
C21A
C22A
H22A
C23A
C24A
H24A
C25A
H25A
C26A
H26A
C31A
C32A
H32A
C33A
C34A
H34A
C35A
H35A
C36A
H36A
C41A
C42A
H42A
C43A
C44A
H44A
0.42665 (17)
0.51917 (18)
0.5753
0.7263 (3)
0.7150 (4)
0.6695
0.15232 (5)
0.17196 (5)
0.1636
0.0275 (5)
0.0339 (6)
0.041*
0.5304 (2)
0.5937
0.7688 (4)
0.7587
0.20333 (6)
0.2164
0.0409 (6)
0.049*
0.4496 (2)
0.4576
0.8374 (4)
0.8785
0.21572 (6)
0.2371
0.0419 (7)
0.050*
0.3572 (2)
0.3011
0.8456 (4)
0.8894
0.19677 (5)
0.2053
0.0396 (6)
0.048*
0.34562 (18)
0.2815
0.7908 (3)
0.7970
0.16549 (5)
0.1528
0.0324 (5)
0.039*
0.41579 (16)
0.49255 (16)
0.5506
0.6744 (3)
0.7142 (3)
0.7761
0.11825 (5)
0.10122 (5)
0.1116
0.0253 (5)
0.0261 (5)
0.031*
0.48663 (16)
0.39996 (17)
0.3941
0.6657 (3)
0.5785 (3)
0.5452
0.06951 (5)
0.05429 (5)
0.0326
0.0259 (5)
0.0306 (5)
0.037*
0.32251 (17)
0.2636
0.5406 (3)
0.4818
0.07084 (5)
0.0604
0.0325 (5)
0.039*
0.33005 (17)
0.2764
0.5873 (3)
0.5600
0.10237 (5)
0.1134
0.0291 (5)
0.035*
0.57269 (17)
0.66903 (16)
0.6777
0.7040 (3)
0.6970 (3)
0.6626
0.05304 (5)
0.06998 (5)
0.0917
0.0271 (5)
0.0243 (5)
0.029*
0.75358 (17)
0.73898 (19)
0.7948
0.7381 (3)
0.7850 (3)
0.8152
0.05658 (5)
0.02437 (5)
0.0145
0.0261 (5)
0.0309 (5)
0.037*
0.6439 (2)
0.6352
0.7877 (4)
0.8170
0.00687 (5)
−0.0150
0.0363 (6)
0.044*
0.56147 (18)
0.4967
0.7482 (4)
0.7512
0.02089 (5)
0.0086
0.0325 (6)
0.039*
0.85465 (17)
0.86803 (17)
0.8116
0.7337 (3)
0.7796 (3)
0.8152
0.07602 (5)
0.10822 (5)
0.1174
0.0248 (5)
0.0254 (5)
0.030*
0.96152 (17)
1.04363 (17)
1.1082
0.7749 (3)
0.7258 (3)
0.7238
0.12728 (5)
0.11342 (5)
0.1259
0.0265 (5)
0.0309 (5)
0.037*
Acta Cryst. (2012). C68, o492–o497
sup-2

supplementary materials
C45A
H45A
C46A
H46A
C51A
C52A
H52A
C53A
H53A
C54A
H54A
C55A
H55A
C56A
H56A
C11B
C12B
H12B
C13B
H13B
C14B
H14B
C15B
H15B
C16B
H16B
C21B
C22B
H22B
C23B
C24B
H24B
C25B
H25B
C26B
H26B
C31B
C32B
H32B
C33B
C34B
H34B
C35B
H35B
C36B
H36B
C41B
C42B
H42B
1.03228 (18)
1.0890
0.6799 (4)
0.6464
0.08169 (5)
0.0725
0.0336 (6)
0.040*
0.93914 (18)
0.9323
0.6825 (3)
0.6489
0.06326 (5)
0.0416
0.0309 (5)
0.037*
0.97332 (17)
0.91403 (18)
0.8646
0.8216 (3)
0.9567 (4)
1.0196
0.16150 (5)
0.17280 (5)
0.1584
0.0285 (5)
0.0329 (5)
0.039*
0.9262 (2)
0.8852
1.0006 (4)
1.0930
0.20470 (5)
0.2120
0.0421 (7)
0.051*
0.9979 (2)
1.0062
0.9097 (4)
0.9393
0.22598 (6)
0.2479
0.0436 (7)
0.052*
1.0573 (2)
1.1070
0.7761 (4)
0.7143
0.21525 (5)
0.2298
0.0398 (6)
0.048*
1.04489 (18)
1.0858
0.7315 (4)
0.6382
0.18329 (5)
0.1762
0.0337 (6)
0.040*
1.23715 (18)
1.16226 (19)
1.0981
0.2329 (3)
0.2218 (3)
0.1773
0.15439 (5)
0.17298 (5)
0.1639
0.0304 (5)
0.0337 (6)
0.040*
1.1797 (2)
1.1277
0.2747 (4)
0.2659
0.20446 (5)
0.2168
0.0418 (7)
0.050*
1.2732 (2)
1.2849
0.3407 (4)
0.3792
0.21809 (6)
0.2396
0.0465 (7)
0.056*
1.3488 (2)
1.4130
0.3497 (4)
0.3928
0.20014 (6)
0.2094
0.0464 (7)
0.056*
1.33127 (19)
1.3841
0.2963 (4)
0.3027
0.16878 (6)
0.1567
0.0385 (6)
0.046*
1.21749 (17)
1.12411 (17)
1.0748
0.1790 (3)
0.2146 (3)
0.2758
0.12044 (5)
0.10239 (5)
0.1121
0.0278 (5)
0.0272 (5)
0.033*
1.10068 (17)
1.17384 (19)
1.1597
0.1635 (3)
0.0753 (3)
0.0389
0.07061 (5)
0.05660 (5)
0.0350
0.0276 (5)
0.0335 (6)
0.040*
1.26747 (19)
1.3169
0.0403 (4)
−0.0201
0.0923 (3)
0.0689
0.07411 (6)
0.0643
0.0351 (6)
0.042*
1.28958 (18)
1.3542
0.10552 (5)
0.1171
0.0329 (5)
0.039*
0.99907 (18)
0.91739 (17)
0.9279
0.2009 (3)
0.1939 (3)
0.1582
0.05315 (5)
0.06889 (5)
0.0905
0.0286 (5)
0.0259 (5)
0.031*
0.82084 (18)
0.8064 (2)
0.7415
0.2366 (3)
0.2864 (3)
0.3178
0.05441 (5)
0.02240 (5)
0.0118
0.0285 (5)
0.0356 (6)
0.043*
0.8863 (2)
0.8754
0.2897 (4)
0.3206
0.00617 (5)
−0.0157
0.0404 (7)
0.048*
0.9814 (2)
1.0354
0.2493 (4)
0.2542
0.02097 (5)
0.0094
0.0365 (6)
0.044*
0.73715 (17)
0.75414 (17)
0.8198
0.2329 (3)
0.2748 (3)
0.3068
0.07294 (5)
0.10511 (5)
0.1149
0.0283 (5)
0.0273 (5)
0.033*
Acta Cryst. (2012). C68, o492–o497
sup-3

supplementary materials
C43B
C44B
H44B
C45B
H45B
C46B
H46B
C51B
C52B
H52B
C53B
H53B
C54B
H54B
C55B
H55B
C56B
H56B
0.67802 (17)
0.58204 (19)
0.5288
0.2713 (3)
0.2254 (4)
0.2225
0.12340 (5)
0.10854 (6)
0.1205
0.0300 (5)
0.0375 (6)
0.045*
0.56377 (19)
0.4979
0.1843 (4)
0.1538
0.07672 (6)
0.0669
0.0396 (6)
0.048*
0.63964 (18)
0.6259
0.1867 (4)
0.1569
0.05895 (5)
0.0371
0.0342 (6)
0.041*
0.69879 (17)
0.76721 (18)
0.8021
0.3198 (4)
0.4578 (4)
0.5211
0.15763 (5)
0.16903 (5)
0.1547
0.0311 (5)
0.0331 (6)
0.040*
0.7855 (2)
0.8321
0.5049 (4)
0.6003
0.20080 (5)
0.2080
0.0415 (6)
0.050*
0.7358 (2)
0.7477
0.4127 (4)
0.4449
0.22196 (6)
0.2438
0.0470 (7)
0.056*
0.6686 (2)
0.6347
0.2728 (4)
0.2085
0.21110 (6)
0.2256
0.0477 (7)
0.057*
0.6506 (2)
0.6048
0.2261 (4)
0.1291
0.17936 (6)
0.1723
0.0405 (6)
0.049*
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
C11A
C12A
C13A
C14A
C15A
C16A
C21A
C22A
C23A
C24A
C25A
C26A
C31A
C32A
C33A
C34A
C35A
C36A
C41A
C42A
C43A
C44A
C45A
C46A
C51A
C52A
C53A
C54A
0.0309 (12)
0.0314 (13)
0.0428 (15)
0.0567 (17)
0.0484 (15)
0.0335 (13)
0.0249 (11)
0.0239 (11)
0.0277 (12)
0.0336 (13)
0.0268 (12)
0.0262 (11)
0.0345 (12)
0.0340 (12)
0.0373 (13)
0.0445 (14)
0.0534 (15)
0.0382 (13)
0.0329 (12)
0.0302 (11)
0.0310 (12)
0.0254 (11)
0.0322 (13)
0.0405 (14)
0.0268 (11)
0.0326 (13)
0.0434 (15)
0.0519 (16)
0.0237 (13)
0.0375 (15)
0.0443 (17)
0.0425 (17)
0.0392 (16)
0.0297 (14)
0.0191 (12)
0.0240 (13)
0.0209 (12)
0.0265 (13)
0.0269 (13)
0.0248 (13)
0.0223 (12)
0.0220 (12)
0.0199 (12)
0.0295 (14)
0.0365 (16)
0.0340 (14)
0.0191 (12)
0.0224 (12)
0.0218 (12)
0.0325 (14)
0.0345 (14)
0.0277 (13)
0.0282 (13)
0.0360 (15)
0.0498 (18)
0.0514 (18)
0.0284 (11)
−0.0015 (10)
−0.0010 (11)
−0.0040 (13)
−0.0016 (14)
0.0080 (13)
0.0018 (11)
0.0018 (9)
0.0065 (9)
0.0042 (10)
−0.0011 (11)
0.0094 (12)
0.0177 (11)
0.0064 (10)
0.0004 (9)
−0.0002 (9)
−0.0014 (9)
−0.0041 (9)
−0.0048 (10)
0.0021 (9)
0.0014 (9)
0.0037 (8)
0.0080 (9)
0.0107 (10)
0.0043 (10)
−0.0046 (9)
0.0094 (9)
0.0088 (9)
0.0052 (9)
0.0041 (9)
0.0161 (10)
0.0154 (10)
0.0035 (9)
0.0020 (9)
0.0055 (11)
0.0010 (11)
0.0036 (9)
0.0325 (12)
0.0331 (13)
0.0272 (12)
0.0348 (13)
0.0342 (12)
0.0305 (11)
0.0290 (11)
0.0270 (11)
0.0286 (11)
0.0405 (13)
0.0353 (12)
0.0233 (10)
0.0168 (9)
0.0000 (11)
−0.0004 (11)
−0.0011 (11)
0.0064 (11)
0.0067 (10)
0.0034 (9)
0.0006 (10)
0.0035 (10)
0.0009 (10)
−0.0013 (10)
0.0006 (10)
0.0005 (10)
0.0017 (10)
0.0022 (10)
0.0008 (11)
0.0011 (13)
0.0008 (11)
0.0005 (10)
0.0006 (10)
−0.0013 (10)
−0.0008 (11)
0.0029 (11)
−0.0008 (11)
−0.0040 (10)
0.0054 (11)
0.0016 (13)
−0.0068 (14)
−0.0001 (9)
0.0013 (9)
−0.0014 (10)
0.0000 (10)
0.0050 (10)
−0.0034 (9)
0.0003 (8)
0.0221 (10)
0.0206 (10)
0.0185 (11)
0.0222 (11)
0.0240 (10)
0.0249 (10)
0.0269 (11)
0.0346 (12)
0.0376 (13)
0.0278 (11)
0.0300 (11)
0.0291 (12)
0.0330 (13)
0.0258 (12)
0.0005 (8)
−0.0007 (9)
0.0009 (10)
0.0005 (9)
0.0032 (8)
0.0031 (9)
0.0032 (9)
0.0019 (10)
0.0011 (11)
−0.0001 (10)
0.0015 (10)
−0.0015 (10)
−0.0103 (12)
−0.0051 (11)
Acta Cryst. (2012). C68, o492–o497
sup-4

supplementary materials
C55A
C56A
C11B
C12B
C13B
C14B
C15B
C16B
C21B
C22B
C23B
C24B
C25B
C26B
C31B
C32B
C33B
C34B
C35B
C36B
C41B
C42B
C43B
C44B
C45B
C46B
C51B
C52B
C53B
C54B
C55B
C56B
0.0390 (14)
0.0333 (13)
0.0323 (12)
0.0356 (13)
0.0531 (16)
0.069 (2)
0.0443 (17)
0.0313 (14)
0.0234 (13)
0.0303 (14)
0.0390 (17)
0.0340 (16)
0.0342 (16)
0.0322 (15)
0.0206 (12)
0.0224 (13)
0.0213 (12)
0.0239 (13)
0.0256 (14)
0.0256 (14)
0.0201 (12)
0.0207 (12)
0.0199 (12)
0.0308 (15)
0.0397 (17)
0.0337 (15)
0.0186 (12)
0.0226 (13)
0.0219 (13)
0.0273 (14)
0.0309 (15)
0.0285 (14)
0.0288 (14)
0.0359 (15)
0.0477 (17)
0.0526 (19)
0.0451 (18)
0.0351 (16)
0.0323 (12)
0.0354 (12)
0.0348 (12)
0.0343 (12)
0.0328 (13)
0.0307 (13)
0.0470 (15)
0.0433 (14)
0.0336 (12)
0.0288 (11)
0.0283 (11)
0.0343 (12)
0.0454 (14)
0.0449 (14)
0.0249 (11)
0.0197 (10)
0.0269 (11)
0.0246 (11)
0.0201 (11)
0.0251 (11)
0.0312 (11)
0.0313 (11)
0.0380 (12)
0.0579 (16)
0.0566 (16)
0.0370 (13)
0.0381 (12)
0.0318 (12)
0.0358 (13)
0.0347 (13)
0.0478 (15)
0.0501 (15)
−0.0024 (13)
−0.0008 (11)
−0.0012 (10)
0.0030 (11)
0.0066 (13)
0.0040 (14)
−0.0056 (14)
−0.0026 (12)
−0.0035 (10)
−0.0011 (10)
−0.0022 (10)
−0.0038 (11)
0.0043 (11)
0.0016 (11)
−0.0017 (10)
−0.0023 (10)
−0.0018 (10)
−0.0001 (12)
−0.0001 (13)
−0.0008 (12)
0.0019 (10)
0.0012 (10)
0.0010 (10)
0.0022 (11)
−0.0004 (11)
0.0028 (11)
0.0048 (11)
0.0023 (11)
0.0022 (13)
0.0138 (15)
0.0113 (15)
0.0030 (12)
−0.0056 (11)
0.0022 (10)
0.0030 (10)
0.0033 (10)
0.0049 (12)
−0.0096 (13)
−0.0120 (12)
−0.0014 (11)
0.0097 (9)
0.0062 (11)
0.0021 (10)
0.0081 (10)
0.0018 (10)
0.0049 (11)
0.0015 (11)
0.0093 (12)
0.0108 (11)
0.0065 (9)
0.0513 (17)
0.0375 (14)
0.0308 (12)
0.0323 (12)
0.0353 (13)
0.0460 (14)
0.0393 (14)
0.0302 (12)
0.0416 (13)
0.0359 (12)
0.0368 (13)
0.0478 (15)
0.0599 (17)
0.0523 (16)
0.0321 (12)
0.0267 (11)
0.0293 (12)
0.0276 (12)
0.0261 (13)
0.0330 (13)
0.0282 (12)
0.0326 (13)
0.0414 (15)
0.0562 (17)
0.0569 (18)
0.0411 (15)
0.0106 (9)
0.0020 (9)
0.0112 (9)
0.0011 (9)
0.0176 (11)
0.0215 (11)
0.0121 (10)
0.0083 (9)
0.0008 (10)
0.0066 (11)
0.0072 (10)
−0.0007 (9)
0.0018 (8)
0.0003 (9)
−0.0004 (9)
−0.0050 (10)
0.0023 (11)
0.0113 (11)
−0.0042 (9)
0.0006 (9)
−0.0022 (9)
−0.0012 (10)
−0.0003 (10)
−0.0014 (10)
0.0035 (9)
0.0024 (9)
0.0031 (10)
0.0074 (11)
−0.0094 (11)
−0.0069 (10)
0.0109 (10)
0.0087 (10)
0.0074 (11)
0.0149 (12)
0.0284 (14)
0.0216 (12)
0.0033 (10)
0.0018 (11)
−0.0031 (12)
−0.0018 (10)
0.0047 (10)
0.0035 (10)
−0.0030 (11)
0.0055 (13)
0.0117 (13)
0.0061 (12)
Geometric parameters (Å, º)
C11A—C16A
C11A—C12A
C11A—C21A
C12A—C13A
C12A—H12A
C13A—C14A
C13A—H13A
C14A—C15A
C14A—H14A
C15A—C16A
C15A—H15A
C16A—H16A
C21A—C22A
C21A—C26A
C22A—C23A
1.394 (3)
C11B—C12B
C11B—C16B
C11B—C21B
C12B—C13B
C12B—H12B
C13B—C14B
C13B—H13B
C14B—C15B
C14B—H14B
C15B—C16B
C15B—H15B
C16B—H16B
C21B—C22B
C21B—C26B
C22B—C23B
1.391 (3)
1.397 (3)
1.490 (3)
1.383 (3)
0.9500
1.402 (3)
1.487 (3)
1.384 (3)
0.9500
1.384 (4)
0.9500
1.393 (4)
0.9500
1.381 (4)
0.9500
1.379 (4)
0.9500
1.381 (3)
0.9500
1.380 (4)
0.9500
0.9500
0.9500
1.394 (3)
1.398 (3)
1.392 (3)
1.398 (3)
1.398 (3)
1.396 (3)
Acta Cryst. (2012). C68, o492–o497
sup-5

supplementary materials
C22A—H22A
C23A—C24A
C23A—C31A
C24A—C25A
C24A—H24A
C25A—C26A
C25A—H25A
C26A—H26A
C31A—C32A
C31A—C36A
C32A—C33A
C32A—H32A
C33A—C34A
C33A—C41A
C34A—C35A
C34A—H34A
C35A—C36A
C35A—H35A
C36A—H36A
C41A—C46A
C41A—C42A
C42A—C43A
C42A—H42A
C43A—C44A
C43A—C51A
C44A—C45A
C44A—H44A
C45A—C46A
C45A—H45A
C46A—H46A
C51A—C56A
C51A—C52A
C52A—C53A
C52A—H52A
C53A—C54A
C53A—H53A
C54A—C55A
C54A—H54A
C55A—C56A
C55A—H55A
C56A—H56A
0.9500
C22B—H22B
C23B—C24B
C23B—C31B
C24B—C25B
C24B—H24B
C25B—C26B
C25B—H25B
C26B—H26B
C31B—C32B
C31B—C36B
C32B—C33B
C32B—H32B
C33B—C34B
C33B—C41B
C34B—C35B
C34B—H34B
C35B—C36B
C35B—H35B
C36B—H36B
C41B—C42B
C41B—C46B
C42B—C43B
C42B—H42B
C43B—C44B
C43B—C51B
C44B—C45B
C44B—H44B
C45B—C46B
C45B—H45B
C46B—H46B
C51B—C52B
C51B—C56B
C52B—C53B
C52B—H52B
C53B—C54B
C53B—H53B
C54B—C55B
C54B—H54B
C55B—C56B
C55B—H55B
C56B—H56B
0.9500
1.398 (3)
1.484 (3)
1.386 (3)
0.9500
1.393 (3)
1.484 (3)
1.390 (3)
0.9500
1.379 (3)
0.9500
1.382 (3)
0.9500
0.9500
0.9500
1.391 (3)
1.397 (3)
1.395 (3)
0.9500
1.388 (3)
1.404 (3)
1.391 (3)
0.9500
1.403 (3)
1.486 (3)
1.384 (3)
0.9500
1.400 (3)
1.487 (3)
1.380 (4)
0.9500
1.382 (3)
0.9500
1.374 (4)
0.9500
0.9500
0.9500
1.397 (3)
1.401 (3)
1.395 (3)
0.9500
1.393 (3)
1.402 (3)
1.394 (3)
0.9500
1.390 (3)
1.487 (3)
1.383 (3)
0.9500
1.394 (3)
1.489 (3)
1.377 (3)
0.9500
1.379 (3)
0.9500
1.376 (4)
0.9500
0.9500
0.9500
1.393 (3)
1.396 (3)
1.386 (3)
0.9500
1.392 (3)
1.394 (3)
1.385 (3)
0.9500
1.385 (4)
0.9500
1.383 (4)
0.9500
1.379 (4)
0.9500
1.386 (4)
0.9500
1.389 (3)
0.9500
1.383 (4)
0.9500
0.9500
0.9500
C16A—C11A—C12A
C16A—C11A—C21A
C12A—C11A—C21A
C13A—C12A—C11A
C13A—C12A—H12A
C11A—C12A—H12A
C12A—C13A—C14A
117.9 (2)
121.3 (2)
120.8 (2)
121.1 (2)
119.5
C12B—C11B—C16B
C12B—C11B—C21B
C16B—C11B—C21B
C13B—C12B—C11B
C13B—C12B—H12B
C11B—C12B—H12B
C12B—C13B—C14B
117.7 (2)
120.8 (2)
121.4 (2)
121.1 (2)
119.5
119.5
119.5
120.1 (2)
120.2 (3)
Acta Cryst. (2012). C68, o492–o497
sup-6

supplementary materials
C12A—C13A—H13A
C14A—C13A—H13A
C15A—C14A—C13A
C15A—C14A—H14A
C13A—C14A—H14A
C16A—C15A—C14A
C16A—C15A—H15A
C14A—C15A—H15A
C15A—C16A—C11A
C15A—C16A—H16A
C11A—C16A—H16A
C22A—C21A—C26A
C22A—C21A—C11A
C26A—C21A—C11A
C23A—C22A—C21A
C23A—C22A—H22A
C21A—C22A—H22A
C22A—C23A—C24A
C22A—C23A—C31A
C24A—C23A—C31A
C25A—C24A—C23A
C25A—C24A—H24A
C23A—C24A—H24A
C26A—C25A—C24A
C26A—C25A—H25A
C24A—C25A—H25A
C25A—C26A—C21A
C25A—C26A—H26A
C21A—C26A—H26A
C32A—C31A—C36A
C32A—C31A—C23A
C36A—C31A—C23A
C31A—C32A—C33A
C31A—C32A—H32A
C33A—C32A—H32A
C32A—C33A—C34A
C32A—C33A—C41A
C34A—C33A—C41A
C35A—C34A—C33A
C35A—C34A—H34A
C33A—C34A—H34A
C36A—C35A—C34A
C36A—C35A—H35A
C34A—C35A—H35A
C35A—C36A—C31A
C35A—C36A—H36A
C31A—C36A—H36A
C46A—C41A—C42A
C46A—C41A—C33A
119.9
C12B—C13B—H13B
119.9
119.9
C14B—C13B—H13B
C15B—C14B—C13B
C15B—C14B—H14B
C13B—C14B—H14B
C14B—C15B—C16B
C14B—C15B—H15B
C16B—C15B—H15B
C15B—C16B—C11B
C15B—C16B—H16B
C11B—C16B—H16B
C22B—C21B—C26B
C22B—C21B—C11B
C26B—C21B—C11B
C23B—C22B—C21B
C23B—C22B—H22B
C21B—C22B—H22B
C24B—C23B—C22B
C24B—C23B—C31B
C22B—C23B—C31B
C25B—C24B—C23B
C25B—C24B—H24B
C23B—C24B—H24B
C26B—C25B—C24B
C26B—C25B—H25B
C24B—C25B—H25B
C25B—C26B—C21B
C25B—C26B—H26B
C21B—C26B—H26B
C32B—C31B—C36B
C32B—C31B—C23B
C36B—C31B—C23B
C31B—C32B—C33B
C31B—C32B—H32B
C33B—C32B—H32B
C32B—C33B—C34B
C32B—C33B—C41B
C34B—C33B—C41B
C35B—C34B—C33B
C35B—C34B—H34B
C33B—C34B—H34B
C36B—C35B—C34B
C36B—C35B—H35B
C34B—C35B—H35B
C35B—C36B—C31B
C35B—C36B—H36B
C31B—C36B—H36B
C42B—C41B—C46B
C42B—C41B—C33B
119.9
119.4 (2)
120.3
119.5 (2)
120.3
120.3
120.3
120.6 (2)
119.7
120.2 (3)
119.9
119.7
119.9
120.9 (2)
119.5
121.3 (2)
119.3
119.5
119.3
118.09 (19)
119.79 (19)
122.12 (19)
121.9 (2)
119.0
117.9 (2)
119.8 (2)
122.3 (2)
122.3 (2)
118.8
119.0
118.8
118.6 (2)
119.44 (19)
121.94 (19)
120.0 (2)
120.0
118.3 (2)
122.3 (2)
119.40 (19)
120.2 (2)
119.9
120.0
119.9
120.7 (2)
119.7
120.8 (2)
119.6
119.7
119.6
120.7 (2)
119.7
120.5 (2)
119.8
119.7
119.8
117.8 (2)
119.41 (17)
122.8 (2)
122.98 (18)
118.5
117.5 (2)
119.94 (18)
122.5 (2)
122.97 (19)
118.5
118.5
118.5
117.4 (2)
120.76 (17)
121.83 (19)
120.5 (2)
119.8
117.8 (2)
120.25 (18)
121.9 (2)
120.0 (2)
120.0
119.8
120.0
120.77 (19)
119.6
121.3 (2)
119.3
119.6
119.3
120.5 (2)
119.8
120.3 (2)
119.9
119.8
119.9
117.6 (2)
121.90 (18)
117.9 (2)
120.3 (2)
Acta Cryst. (2012). C68, o492–o497
sup-7

supplementary materials
C42A—C41A—C33A
C43A—C42A—C41A
C43A—C42A—H42A
C41A—C42A—H42A
C44A—C43A—C42A
C44A—C43A—C51A
C42A—C43A—C51A
C45A—C44A—C43A
C45A—C44A—H44A
C43A—C44A—H44A
C46A—C45A—C44A
C46A—C45A—H45A
C44A—C45A—H45A
C45A—C46A—C41A
C45A—C46A—H46A
C41A—C46A—H46A
C56A—C51A—C52A
C56A—C51A—C43A
C52A—C51A—C43A
C53A—C52A—C51A
C53A—C52A—H52A
C51A—C52A—H52A
C54A—C53A—C52A
C54A—C53A—H53A
C52A—C53A—H53A
C55A—C54A—C53A
C55A—C54A—H54A
C53A—C54A—H54A
C54A—C55A—C56A
C54A—C55A—H55A
C56A—C55A—H55A
C55A—C56A—C51A
C55A—C56A—H56A
C51A—C56A—H56A
120.53 (18)
122.1 (2)
118.9
C46B—C41B—C33B
121.73 (19)
122.2 (2)
118.9
C41B—C42B—C43B
C41B—C42B—H42B
C43B—C42B—H42B
C42B—C43B—C44B
C42B—C43B—C51B
C44B—C43B—C51B
C45B—C44B—C43B
C45B—C44B—H44B
C43B—C44B—H44B
C46B—C45B—C44B
C46B—C45B—H45B
C44B—C45B—H45B
C45B—C46B—C41B
C45B—C46B—H46B
C41B—C46B—H46B
C52B—C51B—C56B
C52B—C51B—C43B
C56B—C51B—C43B
C53B—C52B—C51B
C53B—C52B—H52B
C51B—C52B—H52B
C54B—C53B—C52B
C54B—C53B—H53B
C52B—C53B—H53B
C53B—C54B—C55B
C53B—C54B—H54B
C55B—C54B—H54B
C56B—C55B—C54B
C56B—C55B—H55B
C54B—C55B—H55B
C55B—C56B—C51B
C55B—C56B—H56B
C51B—C56B—H56B
118.9
118.9
118.21 (19)
120.8 (2)
121.01 (19)
120.7 (2)
119.7
118.0 (2)
120.6 (2)
121.3 (2)
120.6 (2)
119.7
119.7
119.7
120.4 (2)
119.8
120.9 (2)
119.6
119.8
119.6
121.0 (2)
119.5
120.4 (2)
119.8
119.5
119.8
118.0 (2)
120.5 (2)
121.5 (2)
121.1 (2)
119.5
117.9 (2)
121.5 (2)
120.7 (2)
121.5 (2)
119.2
119.5
119.2
120.0 (2)
120.0
119.8 (3)
120.1
120.0
120.1
119.7 (2)
120.1
119.4 (2)
120.3
120.1
120.3
120.3 (2)
119.9
120.6 (2)
119.7
119.9
119.7
120.9 (2)
119.5
120.7 (3)
119.6
119.5
119.6
C16A—C11A—C12A—C13A
C21A—C11A—C12A—C13A
C11A—C12A—C13A—C14A
C12A—C13A—C14A—C15A
C13A—C14A—C15A—C16A
C14A—C15A—C16A—C11A
C12A—C11A—C16A—C15A
C21A—C11A—C16A—C15A
C16A—C11A—C21A—C22A
C12A—C11A—C21A—C22A
C16A—C11A—C21A—C26A
C12A—C11A—C21A—C26A
C26A—C21A—C22A—C23A
C11A—C21A—C22A—C23A
−1.0 (4)
177.8 (2)
−0.8 (4)
2.2 (4)
C16B—C11B—C12B—C13B
C21B—C11B—C12B—C13B
C11B—C12B—C13B—C14B
C12B—C13B—C14B—C15B
C13B—C14B—C15B—C16B
C14B—C15B—C16B—C11B
C12B—C11B—C16B—C15B
C21B—C11B—C16B—C15B
C12B—C11B—C21B—C22B
C16B—C11B—C21B—C22B
C12B—C11B—C21B—C26B
C16B—C11B—C21B—C26B
C26B—C21B—C22B—C23B
C11B—C21B—C22B—C23B
1.1 (4)
−178.9 (2)
0.2 (4)
−1.2 (4)
1.0 (4)
−1.7 (4)
−0.1 (4)
1.5 (4)
0.3 (4)
−1.3 (4)
178.7 (2)
35.2 (3)
−144.8 (2)
−144.7 (2)
35.3 (3)
1.3 (3)
−177.4 (2)
142.8 (2)
−36.0 (3)
−36.7 (3)
144.5 (2)
−1.5 (3)
178.9 (2)
−178.6 (2)
Acta Cryst. (2012). C68, o492–o497
sup-8

supplementary materials
C21A—C22A—C23A—C24A
C21A—C22A—C23A—C31A
C22A—C23A—C24A—C25A
C31A—C23A—C24A—C25A
C23A—C24A—C25A—C26A
C24A—C25A—C26A—C21A
C22A—C21A—C26A—C25A
C11A—C21A—C26A—C25A
C22A—C23A—C31A—C32A
C24A—C23A—C31A—C32A
C22A—C23A—C31A—C36A
C24A—C23A—C31A—C36A
C36A—C31A—C32A—C33A
C23A—C31A—C32A—C33A
C31A—C32A—C33A—C34A
C31A—C32A—C33A—C41A
C32A—C33A—C34A—C35A
C41A—C33A—C34A—C35A
C33A—C34A—C35A—C36A
C34A—C35A—C36A—C31A
C32A—C31A—C36A—C35A
C23A—C31A—C36A—C35A
C32A—C33A—C41A—C46A
C34A—C33A—C41A—C46A
C32A—C33A—C41A—C42A
C34A—C33A—C41A—C42A
C46A—C41A—C42A—C43A
C33A—C41A—C42A—C43A
C41A—C42A—C43A—C44A
C41A—C42A—C43A—C51A
C42A—C43A—C44A—C45A
C51A—C43A—C44A—C45A
C43A—C44A—C45A—C46A
C44A—C45A—C46A—C41A
C42A—C41A—C46A—C45A
C33A—C41A—C46A—C45A
C44A—C43A—C51A—C56A
C42A—C43A—C51A—C56A
C44A—C43A—C51A—C52A
C42A—C43A—C51A—C52A
C56A—C51A—C52A—C53A
C43A—C51A—C52A—C53A
C51A—C52A—C53A—C54A
C52A—C53A—C54A—C55A
C53A—C54A—C55A—C56A
C54A—C55A—C56A—C51A
C52A—C51A—C56A—C55A
C43A—C51A—C56A—C55A
1.5 (3)
C21B—C22B—C23B—C24B
−0.5 (3)
178.3 (2)
−0.1 (3)
−178.8 (2)
−0.1 (4)
0.9 (4)
−177.2 (2)
−0.5 (3)
178.1 (2)
−0.3 (4)
0.2 (4)
C21B—C22B—C23B—C31B
C22B—C23B—C24B—C25B
C31B—C23B—C24B—C25B
C23B—C24B—C25B—C26B
C24B—C25B—C26B—C21B
C22B—C21B—C26B—C25B
C11B—C21B—C26B—C25B
C24B—C23B—C31B—C32B
C22B—C23B—C31B—C32B
C24B—C23B—C31B—C36B
C22B—C23B—C31B—C36B
C36B—C31B—C32B—C33B
C23B—C31B—C32B—C33B
C31B—C32B—C33B—C34B
C31B—C32B—C33B—C41B
C32B—C33B—C34B—C35B
C41B—C33B—C34B—C35B
C33B—C34B—C35B—C36B
C34B—C35B—C36B—C31B
C32B—C31B—C36B—C35B
C23B—C31B—C36B—C35B
C32B—C33B—C41B—C42B
C34B—C33B—C41B—C42B
C32B—C33B—C41B—C46B
C34B—C33B—C41B—C46B
C46B—C41B—C42B—C43B
C33B—C41B—C42B—C43B
C41B—C42B—C43B—C44B
C41B—C42B—C43B—C51B
C42B—C43B—C44B—C45B
C51B—C43B—C44B—C45B
C43B—C44B—C45B—C46B
C44B—C45B—C46B—C41B
C42B—C41B—C46B—C45B
C33B—C41B—C46B—C45B
C42B—C43B—C51B—C52B
C44B—C43B—C51B—C52B
C42B—C43B—C51B—C56B
C44B—C43B—C51B—C56B
C56B—C51B—C52B—C53B
C43B—C51B—C52B—C53B
C51B—C52B—C53B—C54B
C52B—C53B—C54B—C55B
C53B—C54B—C55B—C56B
C54B—C55B—C56B—C51B
C52B—C51B—C56B—C55B
C43B—C51B—C56B—C55B
0.7 (3)
−1.4 (3)
178.4 (2)
145.9 (2)
−32.8 (3)
−36.0 (4)
145.3 (2)
−1.6 (3)
176.6 (2)
0.9 (3)
−179.8 (2)
32.0 (3)
−146.6 (2)
−147.7 (2)
33.7 (4)
2.2 (3)
−177.5 (2)
−1.2 (3)
178.2 (2)
−0.7 (3)
179.9 (2)
1.4 (4)
−177.8 (2)
0.7 (4)
179.4 (2)
−1.6 (4)
0.9 (4)
−0.3 (4)
−1.5 (4)
178.2 (2)
147.7 (2)
−32.9 (3)
−31.6 (3)
147.7 (2)
−0.2 (3)
179.2 (2)
1.1 (3)
0.7 (3)
−177.4 (2)
30.6 (3)
−148.1 (2)
−149.1 (2)
32.3 (3)
0.2 (3)
−179.4 (2)
−0.5 (4)
−179.1 (2)
0.3 (4)
−179.1 (2)
−1.1 (3)
179.1 (2)
0.1 (4)
178.8 (2)
0.3 (4)
0.9 (4)
−0.6 (4)
0.3 (4)
−0.8 (4)
179.8 (2)
−34.2 (3)
146.1 (2)
145.5 (2)
−34.3 (3)
0.3 (4)
179.9 (2)
35.9 (3)
−142.6 (3)
−143.4 (2)
38.1 (3)
−1.6 (4)
179.1 (2)
0.6 (4)
−179.4 (2)
−0.1 (4)
0.2 (4)
0.5 (4)
−0.5 (4)
0.7 (4)
−0.4 (4)
−0.6 (4)
1.6 (4)
−0.5 (4)
179.1 (2)
−179.0 (2)
Acta Cryst. (2012). C68, o492–o497
sup-9

supplementary materials
Dihedral angles (%) between adjacent planes
Rings
LTA
LTB
RTA
RTB
1–2
2–3
3–4
4–5
36.28 (11)
32.11 (11)
31.54 (11)
34.16 (12)
35.30 (12)
33.91 (11)
30.89 (12)
37.07 (13)
36.25 (9)
32.22 (8)
30.67 (8)
35.68 (10)
36.11 (9)
34.39 (8)
30.51 (9)
35.68 (10)
The angles are measured going from the ring containing atom C11 (ring 1) through to that containing C51 (ring 5) in all molecules.
MOLFIT parameters for overlays of all combinations of molecules from both polymorphs.
Isometricity R.m.s. fit
R.m.s. fit of
bond lengths
(Å)
R.m.s. fit
wghtd) (Å)
Isometricity
index (unit)
R.m.s. fit of Fit Rotation
Molecule
Molecule
index
wghtd)
(unit
weights) (Å)
(
angles (°)
Angle (°)
(
LTA*
RTA*
LTA*
LTA
LTB
LTB*
LTB
RTB
RTA
RTB
RTA
RTB
0.044
0.053
0.036
0.063
0.037
0.061
95.6
94.7
96.4
93.7
96.3
93.9
0.038
96.2
95.1
96.8
94.0
96.4
94.6
0.0045
0.0042
0.0065
0.0066
0.0072
0.0076
0.297
0.270
0.353
0.332
0.316
0.292
179.68
179.79
89.91
0.049
0.032
0.060
0.036
0.054
179.69
-179.72
-90.58
Note: * denotes an inverted molecule.
Coordinates of the centroids of the molecules in the asymmetric units of the LT and RT forms of (I).
Molecule
LTA
LTB
RTA
RTB
x
y
z
Δx
Δy
Δz
0.6876
0.9459
0.3231
0.8220
0.7492
0.2502
0.1872
0.4447
0.1196
0.1187
0.2602
0.2655
0.2583
0.4989
0.4990
0.2575
0.0009
0.0053
Short contacts between molecules
Symmetry
operator for C—H
ring
Ring (pivot
atom)
Polymorph C
H
H···Cg
C···Cg
Angle at H
LT
LT
C53B
H53B
H25B
Cg(C51A) x, y, z
0.95
2.96
2.91
3.801 (3)
3.521 (3)
149
123
x + 1, y - 1,
C25B
C15A
Cg(C21A)
Cg(C11B)
0.95
z
x - 1, y + 1,
z
LT
H15A
0.95
3.00
3.451 (3)
111
LT
LT
C46A
C46B
H46A
H46B
Cg(C31B) x, y, z
Cg(C31A) x, y - 1, z
0.95
0.95
2.95
3.00
3.354 (2)
3.319 (3)
107
101
RT
RT
C53B
C25B
H53B
H25B
Cg(C51A) x, y - 1, z
0.97
1.03
3.03
2.97
3.867
3.606
145
122
x + 1, y + 1,
Cg(C21A)
z
RT
RT
RT
C15A
C46A
C46B
H15A
H46A
H46B
Cg(C11B) x - 1, y - 1, z 0.95
Cg(C31B) x, y, z 1.00
Cg(C31A) x + 1, y, z 0.99
3.12
2.97
3.06
3.503
3.404
3.346
107
107
98
Cg is the centre of gravity of the ring containing the indicated atom.
Acta Cryst. (2012). C68, o492–o497
sup-10