Two isomorphous complexes: Dichloro[phthalocyaninato(2-)]tin(IV) and dichloro[phthalocyaninato(2-)]-germanium(IV)

Article abstract of DOI:10.1107/S0108270103009417

Isomorphous triclinic forms of dichloro[phthalocyaninato(2-)]tin(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and dichloro[phthalocyaninato(2-)]germanium(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and a monoclinic form of the latter have been obtained from the reaction of pure tin and germanium powder, respectively, with phthalonitrile under a stream of ICl vapour. All three crystal structures consist of centrosymmetric [SnPcCl₂] and [GePcCl₂ [Pc is phthalocyaninate(2-)] molecules, which are separated but interacting. In the triclinic forms (Sn and Ge), the Pc macrocycles are not staggered but slipped, and in the monoclinic form (Ge), the molecules are additionally inclined. In both cases, the central Sn or Ge atom is six-coordinated by the four isoindole N atoms of the Pc macrocyclic ligand and by two Cl atoms (located trans) into a tetragonal-bipyramidal structure. The arrangement of [SnPcCl₂] and [GePcCl₂] molecules in the crystal structure is determined mainly by intermolecular C-H...Cl, π-π and van der Waals interactions.

Full text of DOI:10.1107/S0108270103009417

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
tions of powdered Sn and Ge, respectively, with phthalonitrile
under a stream of ICl vapour at ꢀ433 K, while at ꢀ453 K, the
monoclinic modi®cations of these complexes, (Ib) and (IIb),
are formed (Kubiak & Janczak, 2003). We report here the
crystal structures of the triclinic forms of [SnPcCl2], (Ia), and
[GePcCl2], (IIa), and the monoclinic form of [GePcCl2], (IIb).
ISSN 0108-2701
Two isomorphous complexes:
dichloro[phthalocyaninato(2±)]tin(IV)
and dichloro[phthalocyaninato(2±)]-
germanium(IV)
Jan Janczak* and Ryszard Kubiak
W. Trzebiatowski Institute of Low Temperature and Structures Research, Polish
Academy of Sciences, PO Box 1410, 50-950 Wrocøaw, Poland
Correspondence e-mail: janczak@int.pan.wroc.pl
Received 24 March 2003
Accepted 29 April 2003
Online 31 May 2003
Crystals of (I) and (II) are composed of separate but
interacting [SnPcCl2] and [GePcCl2] molecules (Fig. 1). The
central Sn [in (Ia)] and Ge [in (IIa) and (IIb)] atoms are six-
coordinated by four isoindole N atoms of the phthalo-
cyaninate(2 ) (Pc) macrocyclic ligand and by two Cl atoms
(in a trans geometry) in a slightly distorted square bipyramid.
This geometry agrees with the interpretation of the spectra of
these compounds and related (4+2)-coordinated metallo-
phthalocyaninate complexes (O'Rourke & Curran, 1970;
Fujiki et al., 1986). In both cases, the slightly buckled Pc ring
resides on a crystallographic inversion centre. The largest
displacements from the N4-isoindole plane are observed for
the outermost C atoms, C4 and C5, which are displaced by
Isomorphous triclinic forms of dichloro[phthalocyanin-
ato(2 )]tin(IV), [Sn(C32H16N8)Cl2], and dichloro[phthalo-
cyaninato(2 )]germanium(IV), [Sn(C32H16N8)Cl2], and a
monoclinic form of the latter have been obtained from the
reaction of pure tin and germanium powder, respectively, with
phthalonitrile under a stream of ICl vapour. All three crystal
structures consist of centrosymmetric [SnPcCl2] and
[GePcCl2] [Pc is phthalocyaninate(2 )] molecules, which are
separated but interacting. In the triclinic forms (Sn and Ge),
the Pc macrocycles are not staggered but slipped, and in the
monoclinic form (Ge), the molecules are additionally inclined.
In both cases, the central Sn or Ge atom is six-coordinated by
the four isoindole N atoms of the Pc macrocyclic ligand and by
two Cl atoms (located trans) into a tetragonal±bipyramidal
structure. The arrangement of [SnPcCl2] and [GePcCl2]
molecules in the crystal structure is determined mainly by
intermolecular CÐHÁ Á ÁCl, ꢀ±ꢀ and van der Waals interac-
tions.
Ê
ꢀ0.53, ꢀ0.42 and ꢀ0.21 A in (Ia), (IIa) and (IIb), respectively.
The SnIV and GeIV atoms are located at the centre of the
N4-isoindole square. The SnÐN and GeÐN distances in (Ia)
and (IIa) are comparable to those found in (Ib) (Rogers &
Osborn, 1971) and (IIb), as well as to the distances observed in
È
other Sn and Ge phthalocyaninate complexes (Kramer, 1985;
Ejsmont & Kubiak, 1997; Janczak & Kubiak, 1999c; Janczak,
Razik & Kubiak, 1999).
In (Ia) and (IIa), the axially coordinated Cl atoms are at
Comment
Ê
comparable distances from the Sn and Ge atoms [2.470 (1) A
Ê
in (Ia) and 2.475 (1) A in (IIa); Tables 1 and 2]. However, in
the monoclinic modi®cations of these complexes, the axial
Continuing our investigation of the synthesis and character-
ization of metallophthalocyaninate complexes under a stream
of halogen vapour (I2, IBr and ICl), we have obtained several
metallophthalocyaninate complexes. Iodine-doped metallo-
phthalocyaninate complexes have been reported previously
(Kubiak & Janczak, 1997; Janczak et al., 1998, 2000; Janczak &
Kubiak, 1999a,b,d; Janczak, Kubiak & Hahn, 1999; Janczak,
Kubiak & Jezierski, 1999; Janczak, Razik & Kubiak, 1999;
Janczak & Idemori, 2001a,b, 2002; Janczak, 2003). Recently,
we reported two NbV±diphthalocyaninate complexes,
containing two inter-ring ꢁ CÐC bonds, obtained under IBr
vapour (Janczak & Kubiak, 2003), and an [SbPcCl] complex
obtained under ICl vapour (Janczak & Kubiak, 2001).
Figure 1
A view of the molecular structure of (I) and (II), showing displacement
ellipsoids at the 50% probability level. H atoms are shown as spheres of
arbitrary radii.
Isomorphous triclinic crystals of [SnPcCl2], (Ia), and
[GePcCl2], (IIa), have been obtained directly from the reac-
Acta Cryst. (2003). C59, m237±m240
DOI: 10.1107/S0108270103009417
# 2003 International Union of Crystallography m237

metal-organic compounds
causes a slight tilt of the SnÐCl [1.3 (1)ꢂ in (Ia) and 2.5ꢂ in
(Ib); Rogers & Osborn, 1971] and GeÐCl [0.9 (1)ꢂ in (IIa) and
1.2 (1)ꢂ in (IIb)] axes from the normal to the N2/M/N4 plane
(M = Sn and Ge). The CÐHÁ Á ÁCl intermolecular interactions
link the [SnPcCl2] and [GePcCl2] molecules into two-dimen-
sional sheets, the distance between the halves of the Pc rings of
Ê
SnÐCl and GeÐCl distances are different, viz. 2.448 (2) A in
Ê
(Ib) (Rogers & Osborn, 1971) and 2.299 (1) A in (IIb)
(Table 3). Thus, in the triclinic modi®cation, the GeÐCl bond
is longer than that in the monoclinic modi®cation, which
indicates the different character of the GeÐCl bond in these
forms; the longer GeÐCl bond in the triclinic form is more
ionic than the shorter bond in the monoclinic modi®cation.
The SnÐCl bond lengths in (Ia) and (Ib) are comparable,
which implies that these bonds have the same character in
both forms. The differences between the GeÐCl bonds of
(IIa) and (IIb) are consistent with far-IR spectroscopy, which
shows the GeÐCl band at a higher frequency for the mono-
clinic modi®cation (shorter GeÐCl bond) than for the triclinic
modi®cation (longer GeÐCl bond), while the SnÐCl vibra-
tional bands are observed at almost the same frequency in (Ia)
and (Ib) (Kubiak & Janczak, 2003).
The most remarkable feature of (Ia) and (IIa) is that the Pc
macrocycles are not staggered but slipped. In the monoclinic
form, the molecules are additionally inclined, the angle
between the N4-isoindole planes of two neighbouring Pc
macrocycles being 19.2 (2)ꢂ. In the unit cell (Figs. 2a and 2b)
there are signi®cant intermolecular C14ÐH14Á Á ÁCli [sym-
metry code: (i) 1 x, 1 + y, 1 z] hydrogen-bonding inter-
Ê
neighbouring molecules being less than ꢀ3.4 A. This value
indicates a ꢀ±ꢀ interaction between the phenyl rings of
neighbouring Pc macrocycles, since this distance is shorter
than the van der Waals distance for an aromatic C atom
(Pauling, 1960). This ꢀ±ꢀ interaction (Figs. 2a and 2b) is
signi®cant and, together with the van der Waals and CÐ
HÁ Á ÁCl interactions, is responsible for the molecular
arrangement and the crystal packing. Such intermolecular ꢀ±ꢀ
interactions are a common feature in the ®eld of phthalo-
cyanine chemistry, since the molecules of phthalocyanine and
its metal complexes tend to aggregate as a result of strong ꢀ±ꢀ
intermolecular interactions (Nevin et al., 1987; Terekhov et al.,
1996; Isago et al., 1997, 1998). The solubility of the [SnPcCl2]
and [GePcCl2] complexes in polar solvents, such as water,
methanol and ethanol, is insigni®cant, but the complexes are
slightly soluble in pyridine, dimethylformamide, dimethyl
sulfoxide, tetrahydrofuran and high-boiling aromatic solvents,
such as chloronaphthalene or quinoline. As can be seen from
the crystal structures of [SnPcCl2] and [GePcCl2], molecules
with polar SnÐCl and GeÐCl bonds on both sides of the Pc
ring are surrounded by the hydrophobic peripheral phenyl
rings of neighbouring molecules, which prevent the interac-
tions of polar solvents with the polar SnÐCl or GeÐCl bonds,
thus leading to the limited solubility of the crystals in polar
solvents.
i
i
Ê
actions, with H14Á Á ÁCl distances of 2.83 and 2.89 A, C14Á Á ÁCl
i
Ê
distances of 3.679 (2) and 3.747 (2) A, and C4ÐH4Á Á ÁCl
angles of 153 and 154ꢂ in (Ia) and (IIa), respectively. The
corresponding C4ÐH4Á Á ÁClii [symmetry code: (ii)
x,
z] hydrogen-bonding interactions in (IIb) exhibit
1
2
1
2
12 + y,
H4Á Á ÁClii distances of 2.87 A, C4Á Á ÁClii distances of
Ê
ii
ꢂ
Ê
3.579 (2) A and C4ÐH4Á Á ÁCl angles of 134 . This interaction
Experimental
Triclinic and monoclinic crystals of [SnPcCl2] and [GePcCl2] were
obtained by the direct reaction of pure powdered tin or germanium
with phthalonitrile under a stream of ICl vapour at ꢀ433 and ꢀ453 K,
respectively (Kubiak & Janczak, 2003). At these temperatures, the
liquid 1,2-dicyanobenzene undergoes catalytic tetramerization, with
the simultaneous transfer of two electrons from the Sn or Ge atom to
the Pc ring; the other two electrons are transferred from the Sn or Ge
atom to ICl to form I and Cl ions. Crystals of [SnPcCl2] and
[GePcCl2] were grown, together with crystals of their iodine analo-
gues, viz. [SnPcI2] and [GePcI2].
Triclinic compound (Ia)
Crystal data
3
[Sn(C32H16N8)Cl2]
Mr = 702.12
Triclinic, P1
Dm = 1.74 Mg m
Dm measured by ¯otation in
CHCl3/CHBr3
Ê
a = 7.363 (1) A
Mo Kꢂ radiation
Cell parameters from 2604
re¯ections
Ê
b = 8.676 (2) A
Ê
c = 11.048 (2) A
ꢂ = 74.21 (3)ꢂ
ꢃ = 80.33 (3)ꢂ
ꢄ = 85.47 (3)ꢂ
V = 669.1 (2) A
Z = 1
Dx = 1.743 Mg m
ꢅ = 3.7±27.6ꢂ
1
Figure 2
ꢆ = 1.20 mm
T = 293 (2) K
A view of the molecular packing in the unit cell, showing the
intermolecular CÐHÁ Á ÁCl interactions between the [MIVPcCl2] mol-
ecules [M = Sn in (I) and Ge in (II)] in the triclinic form (a) and in the
monoclinic form (b).
3
Ê
Parallelepiped, violet
0.36 Â 0.18 Â 0.12 mm
3
ꢁ
m238 Janczak and Kubiak
[Sn(C32H16N8)Cl2] and [Ge(C32H16N8)Cl2]
Acta Cryst. (2003). C59, m237±m240

metal-organic compounds
Data collection
Table 2
Selected geometric parameters (A, ) for triclinic (IIa).
ꢂ
Ê
Kuma KM-4 CCD area-detector
diffractometer
! scans
Absorption correction: analytical
face-indexed (SHELXTL;
Sheldrick, 1990)
Tmin = 0.673, Tmax = 0.870
6020 measured re¯ections
2968 independent re¯ections
2604 re¯ections with I > 2ꢁ(I)
Rint = 0.025
GeÐCl
GeÐN2
2.475 (1)
1.979 (3)
GeÐN4
1.968 (3)
ꢅ
max = 27.6ꢂ
N4iiiÐGeÐN2
N2ÐGeÐN4
89.83 (13)
90.17 (13)
h = 9 ! 9
N2ÐGeÐCl
N4ÐGeÐCl
89.09 (10)
90.71 (11)
k = 10 ! 11
l = 12 ! 14
Symmetry code: (iii) 1 x; y; 1 z.
Re®nement
Re®nement on F2
R[F2 > 2ꢁ(F2)] = 0.030
wR(F2) = 0.078
S = 1.01
2968 re¯ections
w = 1/[ꢁ2(F2o) + (0.0274P)2
+ 0.8816P]
Monoclinic compound (IIb)
where P = (F2o + 2Fc2)/3
(Á/ꢁ)max < 0.001
Crystal data
[Ge(C32H16N8)Cl2]
Mr = 656.02
Monoclinic, P21=n
Dm measured by ¯otation in
CHCl3/CHBr3
3
Ê
Áꢇmax = 0.53 e A
3
Ê
0.54 e A
197 parameters
H-atom parameters constrained
Áꢇmin
=
Mo Kꢂ radiation
Cell parameters from 2102
re¯ections
Ê
a = 9.124 (2) A
Ê
b = 14.810 (3) A
ꢅ = 3.4±29ꢂ
ꢆ = 1.36 mm
T = 293 (2) K
Ê
c = 10.233 (2) A
1
ꢃ = 98.50 (3)ꢂ
V = 1367.6 (5) A
3
Table 1
Selected geometric parameters (A, ) for triclinic (Ia).
Ê
ꢂ
Ê
Z = 2
Dx = 1.593 Mg m
Dm = 1.59 Mg m
Parallelepiped, violet
0.30 Â 0.22 Â 0.18 mm
3
3
SnÐCl
SnÐN2
2.470 (1)
2.063 (2)
SnÐN4
2.047 (3)
N2ÐSnÐCl
N4ÐSnÐCl
91.36 (8)
89.42 (8)
N4ÐSnÐN2iii
N4ÐSnÐCliii
89.91 (10)
90.58 (8)
Data collection
Kuma KM-4 CCD area-detector
diffractometer
! scans
Absorption correction: analytical
face-indexed (SHELXTL;
Sheldrick, 1990)
Tmin = 0.687, Tmax = 0.792
12 868 measured re¯ections
3561 independent re¯ections
2102 re¯ections with I > 2ꢁ(I)
Rint = 0.040
Symmetry code: (iii) 1 x; y; 1 z.
ꢅmax = 29.0ꢂ
h = 12 ! 10
k = 20 ! 20
Triclinic compound (IIa)
l = 13 ! 13
Crystal data
3
[Ge(C32H16N8)Cl2]
Mr = 656.02
Triclinic, P1
Dm = 1.63 Mg m
Dm measured by ¯otation in
CHCl3/CHBr3
Re®nement
Re®nement on F2
R[F2 > 2ꢁ(F2)] = 0.044
wR(F2) = 0.098
S = 1.02
3561 re¯ections
w = 1/[ꢁ2(F2o) + (0.0407P)2
+ 0.2270P]
Ê
a = 7.3650 (10) A
Ê
b = 8.704 (2) A
Mo Kꢂ radiation
Cell parameters from 3082
re¯ections
where P = (F2o + 2Fc2)/3
(Á/ꢁ)max < 0.001
Ê
c = 10.966 (2) A
3
Ê
ꢂ = 73.85 (3)ꢂ
ꢃ = 80.61 (3)ꢂ
ꢄ = 86.39 (3)ꢂ
V = 666.1 (2) A
Z = 1
Dx = 1.635 Mg m
ꢅ = 2.8±28ꢂ
Áꢇmax = 1.04 e A
3
Ê
0.33 e A
1
196 parameters
H-atom parameters constrained
Áꢇmin
=
ꢆ = 1.39 mm
T = 293 (2) K
3
Ê
Parallelepiped, violet
0.36 Â 0.25 Â 0.18 mm
3
Table 3
Selected geometric parameters (A, ) for monoclinic (IIb).
ꢂ
Ê
Data collection
GeÐCl
GeÐN2
2.299 (1)
1.959 (2)
GeÐN4
1.954 (2)
Kuma KM-4 CCD area-detector
diffractometer
! scans
Absorption correction: analytical
face-indexed (SHELXTL;
Sheldrick, 1990)
Tmin = 0.634, Tmax = 0.787
5657 measured re¯ections
3082 independent re¯ections
1936 re¯ections with I > 2ꢁ(I)
Rint = 0.013
N2ÐGeÐCl
N4ÐGeÐCl
N2ÐGeÐN4
88.83 (6)
89.80 (6)
90.02 (8)
N4ÐGeÐN2iv
N4ÐGeÐCliv
N2ÐGeÐCliv
89.98 (8)
90.20 (6)
91.17 (6)
ꢅ
max = 28.0ꢂ
h = 9 ! 9
k = 11 ! 10
l = 14 ! 13
Symmetry code: (iv) x; y; z.
Re®nement
The 960 images for six different runs covered more than 95% of
the Ewald sphere. All H atoms were treated as riding, with CÐH
Ê
distances of 0.93 A.
Re®nement on F2
R[F2 > 2ꢁ(F2)] = 0.053
wR(F2) = 0.151
S = 1.06
3082 re¯ections
197 parameters
H-atoms parameters constrained
w = 1/[ꢁ2(F2o) + (0.0686P)2
+ 0.2297P]
where P = (F2o + 2Fc2)/3
(Á/ꢁ)max < 0.001
Áꢇmax = 0.35 e A
3
Ê
3
Ê
0.29 e A
Extinction correction: SHELXL97
Áꢇmin
=
For all three compounds, data collection: KM-4 Software (Kuma,
2000); cell re®nement: KM-4 Software; data reduction: KM-4 Soft-
ware; program(s) used to solve structure: SHELXS97 (Sheldrick,
1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick,
1997); molecular graphics: SHELXTL (Sheldrick, 1990); software
used to prepare material for publication: SHELXL97.
Extinction coef®cient: 0.110 (10)
ꢁ
Acta Cryst. (2003). C59, m237±m240
Janczak and Kubiak
[Sn(C32H16N8)Cl2] and [Ge(C32H16N8)Cl2] m239

metal-organic compounds
Janczak, J. & Kubiak, R. (1999c). Pol. J. Chem. 73, 1587±1592.
Janczak, J. & Kubiak, R. (1999d). Polyhedron, 18, 1621±1627.
Janczak, J. & Kubiak, R. (2001). Acta Cryst. C57, 55±57.
This research was supported by the Polish State Committee
for Scienti®c Research (grant No. 3 T09A 180 19).
Janczak, J. & Kubiak, R. (2003). Polyhedron, 22, 313±322.
Janczak, J., Kubiak, R. & Hahn, F. (1998). Inorg. Chim. Acta, 281, 195±200.
Janczak, J., Kubiak, R. & Hahn, F. (1999). Inorg. Chim. Acta, 287, 101±104.
Janczak, J., Kubiak, R. & Jezierski, A. (1999). Inorg. Chem. 38, 2043±2049.
Janczak, J., Kubiak, R., Svoboda, I., Jezierski, A. & Fuess, H. (2000). Inorg.
Chim. Acta, 304, 150±155.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GG1161). Services for accessing these data are
described at the back of the journal.
Janczak, J., Razik, M. & Kubiak, R. (1999). Acta Cryst. C55, 359±361.
È
È
Kramer, T. (1985). Thesis, REFO-DRUCK Hans Vogler, Tubingen, Germany.
Kubiak, R. & Janczak, J. (1997). Proc. SPIE Int. Soc. Opt. Eng. 3179, 52±55.
Kubiak, R. & Janczak, J. (2003). In preparation.
References
Ejsmont, K. & Kubiak, R. (1997). Acta Cryst. C53, 1051±1054.
Fujiki, M., Tabei, H. & Isa, K. (1986). J. Am. Chem. Soc. 108, 1532±1536.
Isago, H., Leznoff, C. C., Ryan, M. F., Metcalfe, R. A., Davis, R. & Lever,
A. B. P. (1988). Bull. Chem. Soc. Jpn, 71, 1039±1047.
Isago, H., Terekhov, D. S. & Leznoff, C. C. (1997). J. Porphyrins Phthalo-
cyanines, 1, 135±140.
Janczak, J. (2003). Inorg. Chem. In the press.
Kuma (2000). KM-4 Software. Kuma Diffraction, Wrocøaw, Poland.
Nevin, W. A., Liu, W. & Lever, A. B. P. (1987). Can. J. Chem. 65, 855±858.
O'Rourke, M. & Curran, C. (1970). J. Am. Chem. Soc. 92, 1501±1505.
Pauling, L. (1960). The Nature of the Chemical Bond, 3rd ed., p. 260. Ithaca:
Cornell University Press.
Rogers, D. & Osborn, R. S. (1971). J. Chem. Soc. Chem. Commun. pp. 840±
841.
Janczak, J. & Idemori, Y. (2001a). Acta Cryst. C57, 924±925.
Janczak, J. & Idemori, Y. (2001b). Inorg. Chim. Acta, 325, 85±93.
Janczak, J. & Idemori, Y. (2002). Inorg. Chem. 41, 5095±5065.
Janczak, J. & Kubiak, R. (1999a). Inorg. Chem. 38, 2429±2433.
Janczak, J. & Kubiak, R. (1999b). Inorg. Chim. Acta, 288, 174±180.
Sheldrick, G. M. (1990). SHELXTL. Siemens Analytical X-ray Instruments
Inc., Madison, Winsconsin, USA.
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Terekhov, D. S., Nolan, K. J. M., McArthur, C. R. & Leznoff, C. C. (1996). J.
Org. Chem. 61, 3034±3040.
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m240 Janczak and Kubiak
[Sn(C32H16N8)Cl2] and [Ge(C32H16N8)Cl2]
Acta Cryst. (2003). C59, m237±m240