Influence of chloro-form on crystalline products yielded in reactions of 5,10,15,20-tetra-phenyl-porphyrin with HCl and copper(II) salts

Article abstract of DOI:10.1107/S0108270111054102

Chloro-form was found to occupy the lattice of the protonated porphyrin and to promote crystallization of a different poly-morphic form of a metalloporphyrin. The structure of 5,10,15,20-tetra-phenyl-porphyrin-21,23-diium dichloride chloro-form octa-solvate, C44H32N4 ²⁺·2Cl ^-·8CHCl3, (I), in the solid state is described and compared with related solvates. The porphyrin macrocycle displays a distorted saddle shape, with chloride anions above and below the ring. Seven chloro-form mol-ecules are bound via C - H...Cl hydrogen bonds, while the link with the eighth solvent mol-ecule is weaker. A new monoclinic polymorph of (5,10,15,20-tetra-phenyl-porphyrinato)copper(II), [Cu(C44H28N4)], (II), crystallized from chloro-form, is also presented.

Full text of DOI:10.1107/S0108270111054102

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
tives, porphyrin dications have been found very useful in
elucidating the nature of the structural distortions of por-
phyrin derivatives.
ISSN 0108-2701
Influence of chloroform on crystalline
products yielded in reactions of
5,10,15,20-tetraphenylporphyrin
with HCl and copper(II) salts
Luis Aparici Plaza and Jaroslaw Chojnacki*
Chemical Faculty, Gdansk University of Technology, Narutowicza 11/12, Gdansk
PL-80233, Poland
Correspondence e-mail: jaroslaw.chojnacki@chem.pg.gda.pl
Received 29 September 2011
Accepted 15 December 2011
Online 23 December 2011
Chloroform was found to occupy the lattice of the protonated
porphyrin and to promote crystallization of a different poly-
morphic form of a metalloporphyrin. The structure of 5,10,15,20-
tetraphenylporphyrin-21,23-diium dichloride chloroform octa-
2+
solvate, C44H32N4 Á2ClÀÁ8CHCl3, (I), in the solid state is
described and compared with related solvates. The porphyrin
macrocycle displays a distorted saddle shape, with chloride
anions above and below the ring. Seven chloroform molecules
are bound via C—HÁ Á ÁCl hydrogen bonds, while the link with
the eighth solvent molecule is weaker. A new monoclinic
polymorph of (5,10,15,20-tetraphenylporphyrinato)copper(II),
[Cu(C44H28N4)], (II), crystallized from chloroform, is also
presented.
Comment
The study of the geometrical distortion of porphyrins may
give rise to interesting nanostructured materials. For instance,
it has recently been demonstrated that the puckering of
saddle-distorted porphyrins results in nanochannel materials
in which photochemically induced electron transfer to guest
molecules can be detected (Kojima et al., 2007; Nakanishi et
al., 2008).
Porphyrin molecules upon protonation become nonplanar
largely because of the strain caused by the four-H-atom
interaction at the ring core (Stone & Fleischer, 1968). This
behaviour is observed in several structures of protonated
porphyrins, where the ring is forced to adopt a distorted
geometry described as saddled (sad), ruffled (ruf), domed
(dom), propeller-shaped (pro) or waved (wav). Saddled is the
most common (Senge & Kalisch, 1999). Data on selected
structures of protonated porphyrins are presented in Table 1.
The symmetry of the porphyrin macrocycle deformation was
analysed by Stone & Fleischer (1968) in terms of irreducible
representations of the point group D4h. The distortions can be
classified as: sad B1u, ruf B2u, dom A2u, pro A1u and wav(1) or
wav(2) Eg, respectively. From the symbols one can infer that
Porphyrins and metalloporphyrins have been studied for many
years because of their biochemical relevance as well as their
applications. In biology, these tetrapyrrolic macrocycles fulfil
such diverse roles as molecular binding, light harvesting,
catalysis, and energy and/or electron transfer (Burrell et al.,
2001). From the technological point of view, porphyrins have
been useful in a range of applications, from molecular sensing
to the development of dye-sensitized solar cells (Hagfeldt et
al., 2010). Also, these compounds have been found to possess
a rich macromolecular chemistry, i.e. promoting DNA clea-
¨
vage (Borjesson et al., 2010), serving as the core for metallo-
dendrimers (Newkome et al., 1999) or as the building blocks
for other self-organized nanostructures (Harada & Kojima,
2005).
Much work has been devoted to 5,10,15,20-tetraphenyl-
porphyrin and its derived metal complexes, which is under-
standable given the facile and rapid synthesis of this
porphyrin. On some occasions, protonated porphyrins may be
obtained in parallel with metal complexes. While they do not
share the popularity of their free-base or coordinated rela-
m24 # 2012 International Union of Crystallography
doi:10.1107/S0108270111054102
Acta Cryst. (2012). C68, m24–m28

metal-organic compounds
the local symmetry of the porphyrin molecule can be 2 or 4 for
the first two conformations. Local symmetry 4 is allowed only
for dom and pro, whereas 1 is allowed only for the wav forms.
Obviously, this is true only for porphyrins with full D4h
symmetry. For an analysis of deformations in a less symmetric
molecule, see Sun et al. (2012).
Generally, the presence of substituents on the ꢀ positions
causes the porphyrins to deviate more from planarity than
with meso (i.e. 5,10,15,20-) substituents. Cheng et al. (1997)
compared meso (Ph, mesityl and H) and ꢀ (Et, H) substitution
in several diacid porphyrins. Their octaethyl ꢀ-substituted
porphyrins were less distorted than Ph- or mesityl-substituted
molecules in meso positions. They concluded that the stiffness
of the substituent must also be taken into account as a factor
influencing the distortion. Among the compounds in Table 1,
the ꢀ substitution by stiff Ph groups inevitably leads to a
strongly distorted conformation (Á24 > 0.6 and dihedral angles
between the opposite pyrrole rings close to 90ꢀ). In the present
study, we investigated two new derivatives of meso-tetra-
phenylporphyrin.
molecules have a severe impact on the R indices, building an
appropriate disorder model was crucial. In our attempt, all the
chloroform molecules were restrained to the geometry of a
‘regular’ molecule. In order to define this, the Cambridge
Structural Database (CSD; Allen, 2002) was queried for data
on the mean chloroform geometry observed in crystals. A total
of 4707 examples were found. These provided a statistically
relevant estimation of the mean C—Cl bond length value
˚
˚
(1.737 A, with a sample standard uncertainty of 0.06 A) and
˚
the mean 1,3 ClÁ Á ÁCl distance (2.838 A, with a sample stan-
˚
dard uncertainty of 0.08 A). All the disordered molecules
were restrained to the above-mentioned values, while their
˚
standard uncertainties were shrunk to 0.02 A. One molecule
(C45—Cl3—Cl4—Cl5) had to be split over three positions,
and the other three molecules were disordered over two
positions. It appears all four molecules have some degree of
‘orbiting rotational freedom’ over the acceptor atom and may
interchange, while still being linked to chloride atom Cl2.
In 5,10,15,20-tetraphenylporphyrin-21,23-diium dichloride
chloroform octasolvate, (I) (Fig. 1), two N—H bonds (from N1
and N3) are directed above the mean plane of the molecule
and form hydrogen bonds with chloride ion Cl1 and the
remaining N—H bonds point down to the second chloride ion
(Cl2) (see also Table 2).
Three chloroform molecules bound by a C—HÁ Á ÁCl
hydrogen bond to the Cl1 atom, as well as the stand-alone
molecule, are well ordered. However, the remaining four
chloroform molecules, all linked to the Cl2 atom, display
strong disorder (see Fig. 2a). As the disordered chloroform
Figure 2
Figure 1
A view of the hydrogen bonding of the chloroform solvent molecules to
the chloride anions in (a) 5,10,15,20-tetraphenylporphyrin-21,23-diium
dichloride chloroform octasolvate, (I), and (b) 5,10,15,20-tetrakis(4-
methylphenyl)porphyrin-21,23-diium dichloride chloroform heptasolvate
(Grubisha et al., 2008).
The molecular structure of 5,10,15,20-tetraphenylporphyrin-21,23-diium
dichloride chloroform octasolvate, (I). The chloroform solvent molecules
have been omitted for clarity. Displacement ellipsoids are drawn at the
50% probability level.
C44H32N4 Á2ClÀÁ8CHCl3 and [Cu(C44H28N4)] m25
2+
ꢁ
Acta Cryst. (2012). C68, m24–m28
Aparici Plaza and Chojnacki

metal-organic compounds
Many similarities can be found in the structure of
5,10,15,20-tetrakis(4-methylphenyl)porphyrin-21,23-diium di-
chloride chloroform heptasolvate (Grubisha et al., 2008).
Again, the porphyrin ring is distorted, which manifests itself in
dihedral angles of ca 120ꢀ between opposite pyrrole rings.
More interestingly, the chloroform solvent molecules are
bound to the chloride ions by C—HÁ Á ÁCl hydrogen bonds,
four from one side of the porphyrin ring plane and three from
the other (Fig. 2b), forming a similar pattern to that of (I).
meso-Tetraphenylporphyrindiium dichloride is known to
form ‘binary’ solvates with acetonitrile and water (Larsen et
al., 2004). It forms a similar core with a saddle-distorted
porphyrin and ClÀ anions as acceptors of the N—H bonds
from both sides of the porphyrin plane. The similarity ends
there as the structure is further stabilized by O—HÁ Á ÁCl
hydrogen bonds with water molecules and the remaining two
acetonitrile molecules seem to play a space-filling role only.
Other structures with 22,24-dihydro-5,10,15,20-tetra-
phenylporphyrindiium dications contain a number of combi-
nations of anions and solvents: porphyrin bis(hydrogen
mined so far, viz. a tetragonal form crystallizing in I42d,
determined twice [by Fleischer et al. (1964) at 295 K, d =
1.421 Mg mÀ3, then by Zeller et al. (2004) at 100 K, d =
1.461 Mg mÀ3], and another tetragonal form with symmetry
I4/m [He (2007), d = 1.290 Mg mÀ3 at 290 K]. Other structures
of CuTPP contain additional guest molecules, e.g. benzene and
C78 fullerene (Schwiertz et al., 2009), 4-picoline (Byrn et al.,
1993) or m-xylene (Byrn et al., 1991), C60 fullerene either alone
or accompanied by toluene and C2HCl3 (Konarev et al., 2001).
While the conformation of the 24-membered macrocycle is
saddled (local 4 symmetry) for CuTPP crystallizing in I42d, a
flat core (local 4/m symmetry) is observed in the case of the
I4/m space group. The present monoclinic structure of (II)
(P21/n) (Fig. 3) has local 1 symmetry which only allows for the
wave conformation (Eg-type representation). The deviation of
˚
the macrocycle from flatness is not strong (Á24 = 0.0428 A),
but clearly no fourfold symmetry is present (see Fig. 4). The
same type of conformation with a local centre of inversion is
present in all the solvated structures mentioned above
(excluding Konarev et al., 2001). Comparing the densities of
the known polymorphs with that of (II) (1.394 Mg mÀ3), we
sulfate) methanol disolvate (Senge
& Kalisch, 1999),
porphyrin diperchlorate benzene monosolvate (Cheng et al.,
1997), porphyrin bis(tetrafluoroborate) chloroform mono-
solvate dihydrate (Rayati et al., 2008) and porphyrin diper-
chlorate methanol monosolvate (Senge et al., 1994; Senge &
Kalisch, 1999).
In the case of 22,24-dihydro-5,10,15,20-tetraphenylpor-
phyrin chloride ferrichloride, no solvent is trapped in the
structure (Stone & Fleischer, 1968).
Two X-ray crystal structures for (5,10,15,20-tetraphenyl-
porphyrinato)copper(II) (CuTPP), (II), have been deter-
Figure 4
The linear display of the deviations of the 24 atoms of the macrocycle
from their mean plane for (a) 5,10,15,20-tetraphenylporphyrin-21,23-
diium dichloride chloroform octasolvate, (I), and (b) CuTPP (the
horizontal axis is not to scale), (II).
Figure 3
The molecular structure of CuTPP, (II), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
C44H32N4 Á2ClÀÁ8CHCl3 and [Cu(C44H28N4)]
2+
Acta Cryst. (2012). C68, m24–m28
ꢁ
m26 Aparici Plaza and Chojnacki

metal-organic compounds
see that when CuTPP crystallizes from chloroform it does not
present the most dense packing and probably it is not the most
thermodynamically stable. It follows the Ostwald’s rule of
stages (Ostwald, 1897; Threlfall, 2003), which states that
crystallization often favours the least stable polymorphs.
Although the validity of this rule is questionable, the balance
between kinetics and thermodynamics allows us to obtain the
less dense monoclinic form of CuTPP. Chloroform is generally
disregarded as a solvent, because of its tendency to form
disordered structures. However, it is worth keeping in mind
that chloroform may be helpful when trying to obtain less
stable polymorphs, as in the current case.
Refinement
R[F2 > 2ꢄ(F2)] = 0.095
wR(F2) = 0.261
S = 1.05
12824 reflections
720 parameters
55 restraints
H-atom parameteÀrs3 constrained
˚
Áꢅmax = 3.32 e A
À3
˚
Áꢅmin = À2.09 e A
Compound (II)
Crystal data
3
˚
V = 1611.4 (2) A
Z = 2
[Cu(C44H28N4)]
Mr = 676.24
Monoclinic, P21=n
Mo Kꢁ radiation
ꢃ = 0.72 mmÀ1
T = 120 K
0.53 Â 0.23 Â 0.02 mm
˚
a = 14.5813 (12) A
˚
b = 8.6068 (5) A
˚
c = 14.6191 (11) A
ꢀ = 118.56 (1)ꢀ
Experimental
meso-Tetraphenylporphyrin [H2(TPP)] was synthesized according to
the extensively used method devised by Adler et al. (1967). Chloro-
form was dried over molecular sieves while methanol was dried over
metallic Mg. Both solvents were distilled prior to use.
Data collection
Oxford Diffraction Xcalibur
Sapphire2 (large Be window)
diffractometer
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffrac-
tion, 2006), a multifaceted crystal
model based on expressions
derived by Clark & Reid (1995)]
Tmin = 0.777, Tmax = 0.992
11911 measured reflections
3167 independent reflections
2288 reflections with I > 2ꢄ(I)
Rint = 0.052
H2(TPP) (120 mg, 0.2 mmol) was dissolved in chloroform (8 ml).
Then, a 2 M solution of HCl (0.5 ml) was added to methanol (2.5 ml)
and poured into the porphyrin solution. The resulting green solution
was stirred for 10 min and then left to crystallize slowly at 263 K.
After a few days, a small quantity of [H4(TPP)]Cl2Á8CHCl3 single
crystals, suitable for X-ray analysis, appeared on the bottom of the
flask. This deep-blue product was extremely unstable at room tem-
perature, redissolving after some minutes if left in the solution and
becoming very brittle while turning completely opaque when dried, at
which point no reflections could be taken with the diffractometer (we
suspect this was caused by the loss of the most volatile chloroform
molecules). Therefore, extreme caution had to be observed in order
to pick a fresh and appropriate crystal.
Refinement
R[F2 > 2ꢄ(F2)] = 0.052
wR(F2) = 0.147
S = 0.96
223 parameters
H-atom parameteÀrs3 constrained
˚
Áꢅmax = 0.63 e A
Áꢅmin = À0.48 e A
À3
˚
3167 reflections
All C- and N-bound H atoms were refined in isotropic approx-
˚
imation as riding on their parent atoms, with aromatic C—H = 0.95 A,
˚
˚
methine C—H = 1.00 A and N—H = 0.88 A, and with Uiso(H) =
1.2Ueq(C,N). The disorder in four of the eight chloroform molecules
in (I) required a rather complex model. The solvent molecule
containing atom C46 was ordered, but refined using isotropic Cl
atoms. The three chloroform molecules containing atoms C47, C48
and C49, respectively, were fully ordered and were refined with
anisotropic displacement parameters for the non-H atoms. The
chloroform molecule containing atom C45 was refined as being
disordered over three positions. The anisotropic displacement para-
meters of each disordered position for atom C45 were constrained to
be equal, while isotropic displacement parameters were refined for
the Cl atoms in all three orientations and constrained to be equal in
one orientation. A SUMP restraint (Sheldrick, 2008) in the form of
sof(1) + sof(2) + sof(3) = 1.000 (1) was applied and gave a final
distribution of the parts as 0.734 (6)/0.191 (5)/0.077 (4). Notably, the
omission of the third orientation of this chloroform molecule results
in a substantial increase of the R1 index by ca 0.7%. The three solvent
molecules containing atoms C50, C51 and C52 were found to be
disordered and were refined as being split over two orientations with
final occupation-factor ratios of 0.529 (19):0.471 (19), 0.904 (4):
0.096 (4) and 0.587 (14):0.413 (14), respectively. Isotropic displace-
ment parameters were refined for all non-H atoms of these solvent
molecules, except for those of the Cl atoms of the minor orientation
of the molecule containing atom C51, which were kept fixed at
(5,10,15,20-Tetraphenylporphyrinato)copper(II) (CuTPP), (II),
was synthesized by refluxing CuCl2Á2H2O (234 mg) in dimethyl-
formamide (50 ml) in the presence of H2(TPP) (425 mg) over a
period of 2.5 h. The product was completely dried, washed twice with
water and purified by chromatography on an alumina column, using
chloroform as the eluent. The resulting red phase containing CuTPP
was left open to the atmosphere at room temperature. After a few
days, the chloroform had evaporated, leaving well formed crystals of
(II).
Compound (I)
Crystal data
C44H32N4 Á2ClÀÁ8CHCl3
2+
ꢂ = 76.356 (2)ꢀ
V = 3452.31 (15) A
Z = 2
Mo Kꢁ radiation
ꢃ = 1.06 mmÀ1
T = 120 K
0.49 Â 0.40 Â 0.22 mm
3
˚
Mr = 1642.58
Triclinic, P1
a = 11.6031 (3) A
˚
˚
b = 12.6132 (3) A
˚
c = 24.5118 (6) A
ꢁ = 87.706 (2)ꢀ
ꢀ = 82.025 (2)ꢀ
Data collection
Oxford Diffraction Xcalibur
Sapphire2 (large Be window)
diffractometer
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffrac-
tion, 2006), a multifaceted crystal
model based on expressions
derived by Clark & Reid (1995)]
Tmin = 0.705, Tmax = 0.823
22549 measured reflections
12824 independent reflections
9236 reflections with I > 2ꢄ(I)
Rint = 0.030
2
˚
0.04 A . In addition, the isotropic displacement parameters of the two
disordered C-atom positions of each of these solvent molecules were
constrained to be equal. The C—Cl and ClÁ Á ÁCl distances in all of the
disordered chloroform molecules were restrained to 1.737 (2) and
˚
2.848 (2) A, respectively, as described in the Comment. Despite the
C44H32N4 Á2ClÀÁ8CHCl3 and [Cu(C44H28N4)] m27
2+
ꢁ
Acta Cryst. (2012). C68, m24–m28
Aparici Plaza and Chojnacki

metal-organic compounds
Table 1
software used to prepare material for publication: WinGX (Farrugia,
1999), publCIF (Westrip, 2010) and PLATON (Spek, 2009).
Dihedral angles (ꢀ) between the least-squares planes of opposite pyrrole
rings and the average deviation of the 24-membered macrocycle from the
˚
least-squares plane, Á24 (A) (Senge & Kalisch, 1999), in different
protonated porphyrin dichlorides or other salts of protonated meso-
tetraphenylporphyrins [programs used: PLATON (Spek, 2009) and
Mercury (Macrae et al., 2006)].
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FN3092). Services for accessing these data are
described at the back of the journal.
Note that usually programs calculate acute dihedral angles, so the values cited
here are those of the corresponding supplementary ones.
References
Anion
Solvent
py1–py3 py2–py4 Á24 Substitution
Local
symmetry
Adler, A. D., Longo, F. R., Finarelli, J. D., Goldmacher, J., Assour, J. &
Korsakoff, L. (1967). J. Org. Chem. 32, 476.
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
meso
125.5 (4) 126.3 (4) 0.390 Ph
120.32 121.88 0.429 4-MePh
ꢀ
˚
¨
Borjesson, K., Wiberg, J., El-Sagheer, A. H., Ljungdahl, T., Martensson, J.,
Brown, T., Norden, B. & Albinsson, B. (2010). ACS Nano, 9, 5037–5046.
Burrell, A. K., Officer, D. L., Plieger, P. G. & Reid, D. C. W. (2001). Chem. Rev.
101, 2751–2796.
Cla
Clb
Clc
Cld
CHCl3
CHCl3
H2O/MeCN
MeCN/hydro-
quinone
H
H
1
1
1
2
126.4
90.69
111.6 0.446 Ph
90.69 0.64 Ph
H
Ph
Byrn, M. P., Curtis, C. J., Goldberg, I., Hsiou, Yu., Khan, S. I., Sawin, P. A.,
Tendick, S. K. & Strouse, C. E. (1991). J. Am. Chem. Soc. 113, 6549–6557.
Byrn, M. P., Curtis, C. J., Hsiou, Yu., Khan, S. I., Sawin, P. A., Tendick, S. K.,
Terzis, A. & Strouse, C. E. (1993). J. Am. Chem. Soc. 115, 9480–9497.
Cheng, B., Munro, O. Q., Marques, H. M. & Scheidt, W. R. (1997). J. Am.
Chem. Soc. 119, 10732–10742.
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Finikova, O. S., Cheprakov, A. V., Carroll, P. J., Dalosto, S. & Vinogradov, S. A.
(2002). Inorg. Chem. 41, 6944–6946.
Fleischer, E. B., Miller, C. K. & Webb, L. E. (1964). J. Am. Chem. Soc. 86,
2342–2347.
Grubisha, D. S., Mirafzal, G. A. & Woo, L. K. (2008). Inorg. Chim. Acta, 361,
3079–3083.
Hagfeldt, A., Boschloo, G., Sun, L., Kloo, L. & Pettersson, H. (2010). Chem.
Rev. 110, 6595–6663.
Cle
Clf
Clg
Clh
CH2Cl2
Toluene
98.93
103.5
CHCl3/MeOH 131.34 134.29 0.376 Ph
98.23 0.605 Ph
Et
Et
1
4
1
2
103.5
0.556 Ph
Et,H†
Ph
TTF/MeCN,
H2O
MeCN
MeCN/CHCl3, 90.6
H2O
p-xylene/MeCN 90.05
94.13
94.13 0.617 Ph
Cli
Cli
90.35
90.35 0.647 Ph
90.6
Ph
Ph
2
2
0.639 Ph
Cli
90.05 0.644 Ph
Ph
H
H
2
4
1
4
j
Cl, FeCl4 none
Clj
Clk
113.91 113.91 0.524 Ph
0.394 4-py
H2O
tBu–O–Me
126.91 126.1
115.86 115.86 0.496 4-MeO- c-Hexane
COPh
l
BF4
ClO4
CHCl3/H2O
MeOH
131.48 135.06 0.340 Ph
118.56 117.26 0.464 H
H
Me,Et
1
1
m
Harada, R. & Kojima, T. (2005). Chem. Commun. pp. 716–718.
He, H.-S. (2007). Acta Cryst. E63, m976–m977.
Hu, C., Noll, B. C. & Scheidt, W. R. (2007). Acta Cryst. E63, o3128.
Jaquinod, L., Siri, O., Khoury, R. G. & Smith, K. M. (1998). Chem. Commun.
pp. 1261–1262.
† This structure presents a special feature, i.e. it contains three fused porphyrin rings.
References: (a) this work; (b) Grubisha et al. (2008); (c) Larsen et al. (2004); (d) Harada
& Kojima (2005); (e) Senge & Kalisch (1999); (f) Hu et al. (2007); (g) Jaquinod et al.
(1998); (h) Nakanishi et al. (2008); (i) Kojima et al. (2007); (j) Stone & Fleischer (1968);
(k) Finikova et al. (2002); (l) Rayati et al. (2008); (m) Senge et al. (1994).
Kojima, T., Nakanishi, T., Harada, R., Ohkubo, K., Yamauchi, S. & Fukuzumi,
S. (2007). Chem. Eur. J. 13, 8714–8725.
Table 2
Hydrogen-bond geometry (A, ) for (I).
Konarev, D. V., Neretin, I. S., Slovokhotov, Y. L., Yudanova, E. I., Drichko, N.
V., Shul’ga, Y. M., Tarasov, B. P., Gumanov, L. L., Batsanov, A. S., Howard, J.
A. K. & Lyubovskaya, R. N. (2001). Chem. Eur. J. 7, 2605–2616.
Larsen, F. B., Hansen, F. G. & McKenzie, C. J. (2004). Acta Cryst. E60, o497–
o499.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor,
R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.
Nakanishi, T., Kojima, T., Ohkubo, K., Hasobe, T., Nakayama, K. & Fukuzumi,
S. (2008). Chem. Mater. 20, 7492–7500.
Newkome, G. R., He, E. & Moorefield, C. N. (1999). Chem. Rev. 99, 1689–1746.
Ostwald, W. (1897). Z. Phys. Chem. 22, 289–330.
Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon,
Oxfordshire, England.
ꢀ
˚
D—HÁ Á ÁA
D—H
HÁ Á ÁA
DÁ Á ÁA
D—HÁ Á ÁA
N1—H1Á Á ÁCl1
0.88
0.88
0.88
0.88
1.00
1.00
1.00
1.00
1.00
1.00
1.00
2.30
2.38
2.38
2.40
2.64
2.50
2.39
2.63
2.65
2.52
2.70
3.110 (5)
3.183 (6)
3.167 (5)
3.198 (6)
3.382 (10)
3.474 (9)
3.362 (8)
3.492 (8)
3.47 (2)
152
152
148
152
132
166
164
145
140
158
146
N3—H3AÁ Á ÁCl1
N2—H2AÁ Á ÁCl2
N4—H4Á Á ÁCl2
C45—H45Á Á ÁCl2
C46—H46Á Á ÁCl1
C48—H48Á Á ÁCl1
C49—H49Á Á ÁCl1
C50—H50Á Á ÁCl2
C51—H51Á Á ÁCl2
C52—H52Á Á ÁCl2
Rayati, S., Zakavi, S., Ghaemi, A. & Carroll, P. J. (2008). Tetrahedron Lett. 49,
664–667.
¨
Schwiertz, J., Wiehe, A., Grafe, S., Gitter, B. & Epple, M. (2009). Biomaterials,
30, 3324–3331.
3.467 (10)
3.57 (2)
Senge, M. O., Forsyth, T. P., Nguyen, L. T. & Smith, K. M. (1994). Angew.
Chem. Int. Ed. 33, 2485–2487.
Senge, M. O. & Kalisch, W. W. (1999). Z. Naturforsch. Teil B, 54, 943–959.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Stone, A. & Fleischer, E. B. (1968). J. Am. Chem. Soc. 90, 2735–2748.
Sun, L., Jentzen, W. & Shelnutt, J. A. (2012). The Normal Coordinate
Structural Decomposition Engine, http://jasheln.unm.edu.
Threlfall, T. (2003). Org. Process Res. Dev. 7, 1017–1027.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
complex disorder model, the residual electron density (located in the
disordered solvent region) is still high, indicating that the real
structure is perhaps even more complex. This may be the main reason
for the relatively large value of R1.
For both compounds, data collection: CrysAlis PRO (Oxford
Diffraction, 2006); cell refinement: CrysAlis PRO; data reduction:
CrysAlis PRO; program(s) used to solve structure: SHELXS97
(Sheldrick, 2008); program(s) used to refine structure: SHELXL97
(Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006);
Zeller, M., DiMuzio, S. J., Wilcox, R. J. & Hunter, A. D. (2004). Private
communication.
C44H32N4 Á2ClÀÁ8CHCl3 and [Cu(C44H28N4)]
2+
Acta Cryst. (2012). C68, m24–m28
ꢁ
m28 Aparici Plaza and Chojnacki