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The crystal structure of a polymorph of copper phthalocyanine (CuPc) grown on a KCl substrate is redetermined by transmission electron diffraction. It has a triclinic unit cell containing one molecule; the crystal does not have a herringbone-type molecular arrangement, which is a common packing mode of planar phthalocyanines. The molecular packing is determined by the diffraction intensity with the aid of the calculation of molecular packing energy. One of the striking features of this polymorph is its stacking mode within a molecular column: the molecular stacking direction projected on a molecular plane is different by an angle of about 45° from that of the α-modifications of platinum phthalocyanine (PtPc) and metal-free phthalocyanine (H2Pc). A powder X-ray diffraction profile calculated for the polymorph agrees well with that of so-called α-CuPc and Rietveld analysis for α-CuPc indicates that the CuPc crystals grown on KCl are actually α-CuPc; hence, α-CuPc is not isostructural with either α-PtPc or α-H2Pc. On the basis of the present results and the reported crystal structures of the planar phthalocyanines that form molecular columns, the polymorphs of the phthalocyanines can be classified into four types distinguished by the molecular stacking mode within the column: α(×)-, α(+)-, β(×)- and β(+)-types.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010876810300942X/bk0130sup1.cif
Contains datablocks acupc, I

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S010876810300942X/bk0130Isup2.rtv
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S010876810300942X/bk0130sup3.pdf
Supplementary material

CCDC reference: 219250

Computing details top

Data collection: R-AXIS (Rigaku, 1996); program(s) used to refine structure: RIETAN2000 (Izumi, 2002b).

Phthalocyaninato-copper(ii) top
Crystal data top
C32H16CuN8V = 582.3 (5) Å3
Mr = 576.07Z = 1
Triclinic, P1F(000) = 293
Hall symbol: -P 1Dx = 1.643 Mg m3
a = 12.886 (2) ÅCu Kα1, Cu Kα2 radiation, λ = 1.54056, 1.54439 Å
b = 3.769 (3) ŵ = 1.67 mm1
c = 12.061 (3) ÅT = 295 K
α = 96.22 (7)°dark blue
β = 90.62 (4)°cylinder, 5 × 0.3 mm
γ = 90.32 (8)°
Data collection top
Rigaku RU-3V
diffractometer
Specimen mounting: quartz capillary
Radiation source: rotating-anode tubeData collection mode: transmission
Equatorial mounted graphite monochromatorScan method: Stationary detector
Refinement top
Refinement on InetProfile function: pseudo-Voigt
Rp = 0.02483 parameters
Rwp = 0.03368 restraints
Rexp = 0.016H-atom parameters not defined
1807 data points1/yi
Excluded region(s): 60 to 95.8 degrees too small peak intensitiesBackground function: Legendre polynomial
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10000.0317*
C10.2276 (19)0.08 (2)0.036 (3)0.0317*
C20.312 (3)0.04 (2)0.115 (5)0.0317*
C30.419 (4)0.02 (2)0.117 (3)0.0317*
C40.473 (3)0.08 (3)0.217 (7)0.0317*
C50.428 (7)0.32 (3)0.299 (6)0.0317*
C60.322 (3)0.38 (3)0.297 (8)0.0317*
C70.265 (5)0.25 (3)0.204 (7)0.0317*
C80.155 (5)0.22 (3)0.182 (5)0.0317*
C90.016 (4)0.38 (2)0.232 (3)0.0317*
C100.089 (3)0.57 (4)0.308 (7)0.0317*
C110.0762 (19)0.77 (3)0.410 (7)0.0317*
C120.163 (2)0.89 (3)0.467 (6)0.0317*
C130.262 (4)0.83 (3)0.417 (5)0.0317*
C140.272 (4)0.70 (3)0.306 (5)0.0317*
C150.186 (2)0.55 (3)0.253 (5)0.0317*
C160.168 (2)0.34 (3)0.143 (5)0.0317*
N10.245 (2)0.26 (2)0.067 (4)0.0317*
N20.134 (2)0.05 (2)0.077 (5)0.0317*
N30.086 (4)0.37 (3)0.256 (5)0.0317*
N40.064 (2)0.25 (2)0.132 (3)0.0317*
Geometric parameters (Å, º) top
Cu1—N21.95 (3)C8—N31.34 (9)
Cu1—N41.96 (5)C9—C101.47 (10)
C1—N11.36 (7)C9—N31.34 (7)
C1—N21.38 (5)C9—N41.38 (6)
C1—C21.48 (6)C10—C111.38 (13)
C2—C31.40 (7)C10—C151.41 (6)
C2—C71.42 (11)C11—C121.36 (7)
C3—C41.39 (8)C12—C131.41 (7)
C4—C51.41 (12)C13—C141.39 (8)
C5—C61.38 (10)C14—C151.38 (9)
C6—C71.38 (11)C15—C161.48 (10)
C7—C81.44 (9)C16—N1i1.36 (6)
C8—N21.38 (9)C16—N41.38 (5)
N2—Cu1—N4i90.9 (19)C5—C4—C3120 (6)
Cu1—N4i—C16i126 (4)C4—C3—C2118 (5)
N4i—C16i—N1127 (6)C9—N4—C16107 (5)
C16i—N1—C1123 (4)N4—C16—C15110 (4)
N1—C1—N2127 (3)C16—C15—C10106 (5)
C1—N2—Cu1126 (4)C15—C10—C9106 (7)
N2—Cu1—N489.1 (19)C10—C9—N4111 (4)
Cu1—N4—C9127 (3)C10—C15—C14120 (6)
N4—C9—N3127 (5)C15—C14—C13118 (5)
C9—N3—C8122 (6)C14—C13—C12120 (5)
N3—C8—N2128 (5)C13—C12—C11121 (7)
C8—N2—Cu1127 (4)C12—C11—C10118 (4)
C1—N2—C8107 (4)C11—C10—C15121 (7)
N2—C8—C7111 (6)C14—C15—C16134 (4)
C8—C7—C2106 (7)C15—C16—N1i123 (4)
C7—C2—C1106 (4)N1—C1—C2123 (3)
C2—C1—N2110 (4)C1—C2—C3134 (5)
C3—C2—C7120 (5)C11—C10—C9133 (4)
C2—C7—C6120 (6)C10—C9—N3121 (5)
C7—C6—C5119 (7)N3—C8—C7121 (7)
C6—C5—C4120 (7)C8—C7—C6133 (7)
Symmetry code: (i) x, y, z.
 

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