Crystal and molecular structure of dithallium phthalocyanine at 300 K

Journal of Alloys and Compounds, 202 (1993) 69-72 JALCOM 777 69 Crystal and molecular structure of dithallium phthalocyanine at 300 K Jan Janczak and Ryszard Kubiak W. Trzebiatowski Institute for Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 937, 50-950 Wroclaw (Poland) (Received April 7, 1993) Abstract A new complex of dithallium phthalocyanine (Co2HI6NsT]2) in crystalline form has been synthesized. The crystal at room temperature is orthorhombic, space group Cmca, with lattice parameters a=25.173(4) A, b=7.353(2) /~ and c=13.765(3) /~, V=2547.9(7) /~3, Z = 4 , M=921.3, D0(flotation)=2.397 g cm -3, Dc=2.402 g cm -3. The refined crystal structure with anisotropic temperature factors for T1, C and N atoms and isotropic for H atoms gave R = 0.043, wR = 0.040 and S = 1.75. The structure consists of discrete dithallium phthalocyanine molecules. The thallium atoms are displaced above and below the phthalocyanine skeleton plane. The deviation of the TI atoms with the above plane is + 1.844 A,. Details of the molecular structure are compared and discussed with regard to other metallophthalocyanines. 1. Introduction Metallophthalocyanines have been intensively investigated as molecular electrical conductors or semiconductors [1--4]. Among the metals of the main third group, crystal structures of the metallophthalocyanines with AI and Ga are found in the literature. Both of these phthalocyanines have the general formula MePcX, where Pc represents the macrocyclic phthalocyanine ligand and X---CI [5] or F [6--8]. The crystal structure of (A1Pc)20 also has been determined [9]. Using a synthesis method published previously by us [10] we prepared in crystalline form new metallophthalocyanines with metals of the main third group (without chlorides and oxygen anions): dithallium phthalocyanine (T12Pc) and diindium triphthalocyanine (In2Pc3). Here we present the X-ray crystal structure determination of dithallium phthalocyanine. 2. Experimental details 2.1. Data collection Crystals were prepared according to the method described previously [10]. A crystal of approximate dimensions 0.04 mm × 0.07 mm × 0.45 mm was used for data collection on a four-circle Kuma Diffraction KM4 diffractometer with graphite-monochromatized Mo Ka radiation. Preliminary examination by rotation and Weissenberg photographs revealed the following sys0925-8388/93l$6.00 tematic absences: hkl, h + k = 2n + 1; hOl, 1= 2n + 1; hk0, h = 2n + 1. These indicate the space group Cmca, which was used in the structure solution and refinement. Accurate lattice parameters were refined by the leastsquares method fit of 20 reflections measured in the range 18°<20<26 °. A total of 1753 reflections were measured in the range 4° < 20 < 50 ° ((sin 0/h)m~-- 0.595) using the to-20 scan technique with scan speed 0.02°-0.1 ° s- 1 and scan width 1.4 °. The hkl ranges were as follows: h, - 3 0 to 30; k, 0 to 9; l, 0 to 16. Two standard reflections ((232) and (230)) were monitored every 50 reflections. They exhibited no significant intensity variations. The measured intensities were corrected for Lorentz and polarization effects. Face-indexed numerical absorption was applied (the distances between the faces are equal: (100)-(i00), 0.04 mm; (010)-(0i0), 0.45 ram; (001)-(00i), 0.07 mm). The minimum and maximum transmission factors are 0.39182 and 0.58597 respectively. 1036 independent reflections (521 with F>4trv), Rant=0.035, were used in the calculations. The crystal data were as follows: C32H16N8T12, Mr=921.3, orthorhombic, Cmca, a=25.173(4) /~, b -- 7.353(2)/~, c = 13.765(3)/~ V= 2547.9(7)/~3, Z = 4, Do(flotation) = 2.397 g c m -a, Dc = 2.402 g cm -3, A(Mo Ka)=0.710 73 /~, /z(Mo K a ) = 128.0 cm -1, T=300 K, F(000) = 1704. 2.2. Structure determination and refinement The structure was solved by the three-dimensional Patterson method (TI atom). The remaining non-hy© 1993- Elsevier Sequoia. All rights reserved 70 J. Janczak, R. Kubiak / Crystalline dithallium phthalocyanine TABLE 1. Final atomic coordinates and equivalent isotropic thermal parameters with estimated standard deviations in parentheses T1 N(1) N(2) N(3) C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) H(3) H(4) H(5) H(6) xXl04 yXl04 zXl04 U,q ( x l 0 -a /~-2)a 0 1326(7) 548(6) 0 1082(6) 1358(6) 1910(6) 2055(7) 1651(7) 1139(6) 979(6) 464(6) 2220(8) 2415(7) 1712(14) 880(8) 1170(2) 0 1726(10) 4055(11) 1439(12) 2977(12) 3302(12) 4897(13) 5928(12) 5631(12) 4070(12) 3248(13) 2610(14) 5327(13) 6802(14) 6544(14) 1185(8) 0 -478(8) -1205(11) -395(9) -836(10) -920(9) -1433(9) -1826(9) -1740(9) -1148(10) -978(9) -754(14) -1466(14) -2332(11) -1899(14) 39(2) 27(3) 27(3) 26(3) 27(3) 29(3) 39(3) 36(3) 37(3) 22(4) 39(3) 28(3) 77(3) 72(4) 73(3) 78(4) drogen atoms (C and N) were located from different Fourier calculations. The structure was refined by the full-matrix least-squares method with anisotropic temperature factors (using the SrIELXXL program system [11]). The hydrogen atoms' positions were calculated with geometrical correlations. The function minimized was Ew(IF01-IFol) with the weighting scheme w = 1/ o,2. The final results were R=0.043, wR=0.040 and S = 1.75, with largest and mean A/o'values of 0.198 and 0.037 respectively. The residual electron density in the final difference Fourier synthesis was within the range - 1 . 0 8 to 1.15 e - /~-3. Scattering factors for neutral atoms and corrections for anomalous dispersion were as in the SHELXTL PC program system, which was also used for all the structure calculations and drawing preparation. Final positional and isotropic thermal parameters are given in Table 1. Bond lengths and angles are collected in Table 2. aEquivalent isotropic Ueq defined as one-third of the trace of the orthogonalized U,-~tensor. 3. Results and discussion TABLE 2. Bond lengths (hngstrrms) and angles (degrees) with estimated standard deviations in parentheses TI-N(2) 2.704(12) x 2 Tl-Tli 3.689(3) C(1)-N(2) 1.366(18) C(2)-C(3) 1.415(19) C(4)-C(5) 1.380(20) C(6)-C(7) 1.464(16) C(7)-C(2) 1.319(20) C(8)-N(3) 1.347(16) N(2)-TI-N(2) ~ 94.3(3) N(2)-T1-N(2) ~i 63.7(3) N(2)'-TI-N(2) ~' 61.0(5) N(2)-TI-N(2) ~i 61.4(5) TI-N(2)-TI ~ 47.0(3) N(1)-C(1)-N(2) 127.4(13) N(1)-C(1)-C(2) 124.3(15) N(2)-C(1)--C(2) 108.3(11) C(1)-N(2)-C(8) 109.3(12) C(1)-C(2)-C(3) 129.2(13) C(1)-C(2)-C(7) 105.3(12) C(2)-C(3)-C(4) 115.7(12) C(3)-C(4)-C(5) 117.4(13) C(4)-C(5)-C(6) 126.6(12) C(5)-C(6)-C(7) 115.7(12) C(2)-C(7)-C(6) 117.5(14) C(3)-C(2)-C(7) 125.5(11) C(6)-C(7)-C(8) 131.4(13) C(2)-C(7)-C(8) 109.9(11) C(7)--C(8)-N(3) 123.7(9) N(2)-C(8)-C(7) 106.9(13) C(7)-C(8)-N(3) 123.7(9) N(2)-C(8)-N(3) 128.9(13) TI-N(2) i N(1)--C(1) C(1)-C(2) C(3)-C(4) C(5)-C(6) C(7)-C(8) C(8)--N(2) 2.718(11)x 2 1.338(15) 1.459(13) 1.417(15) 1.313(22) 1.450(21) 1.331(14) Symmetry codes: i, -x, -y, -z; ii, x, -y, -z; iii, -x, y, z. The dithallium phthalocyanine molecular geometry and numbering of the atoms used in this paper are illustrated in Fig. 1. The macromolecule is non-planar. The peripheral benzene rings in the macrocyclic ligand are not perfectly hexagonal. The dimension of the benzene ring is normal with a mean C--C bond length of 1.385/~ and mean angle 120° and, as with the central 16-membered ring, all the bonds are equivalent. The C-C bonds in the isoindole ring, with mean length 1.455/k, have a bond order of 1.25 and are therefore obviously linked with the ~- electron resonating system. This value is comparable with those for the metal-free (5) Fig. 1. Molecular geometry and mJmbering of the atoms. J. Janczalg R. K u b i a k / Crystalline dithallium phthalocyanine " ~., ~ X J f Q~,~9,.~ .__: 71 ' ~ ~'~-' I ~ x - T ~ ' - 7 Fig. 2. Arrangement of TI2Pc and stereopacking view in the unit cell. phthalocyanine [12-14] and the other metallophthalocyanines [5, 6, 15-17]. A full treatment of the phthalocyanine molecule by both valence bond and molecular orbital theories would be of value. The mean C-N bond length in the central 16-membered ring is 1.345 /~ which is exactly that required for a bond order of 1.5. The C-N bond attached to N(1) and N(3) of length 1.342 /k is a little shorter than that attached to N(2), i.e. 1.349 ~. This could be due to the influence of the thallium atoms attracting N(2), but is more likely to be due to the 5-membered isoindole ring diverting some of the 7r electrons away from the N(2) branches. This small difference in C-N distances is also visible in the other non-planar phthalocyanines [17-19]. The equation of the mean plane through the macrocyclic ligand, referred to the standard orthogonal axes, is O.OXo+O.4597Yo+O.8881Zo=O. The average displacement of the carbon and nitrogen atoms out of this plane is 0.049 /~,, randomly below and above. The most interesting and peculiar feature of this structure is the presence of two metal ions per phthalocyanine macromolecule. The present structure is unique among metallophthalocyanines, and there are no similar examples in the literature. The two thallium cations are linked to the same four isoindole nitrogen atoms and form an octahedron. The thallium ions occupied two opposite corners of this octahedron. The mean T1-N bond length is 2.711(10) ~, and the N(2)-N(2) i and N(2)-N(2)" distances are 2.755(6) /~ and 2.859(6) /~ respectively (where i denotes - x , y, z and ii x, - y , z). The displacements of the thallium cations with respect to the N-isoindole plane are equal to within _+1.845 /~. The four N-T1-N base angles have a mean of 62.1(5) °, and the two obtuse N-TI-N angles are 94.2(3) °. The four TI-N-T1 angles are equal at 85.8(3) °. The intramolecular T1-T1 bond distance of 3.689(3)/~ indicates a weak interaction between these atoms, and is only about 0.25 /~ longer than in pure metal (T1-T1 distances in pure metal are 3.408(6) and 3.457(6) ~). Thus the molecular geometry of the T12Pc is considerably distorted from D4h point symmetry. This deviation probably arises from the intermolecular interaction in the crystal. The macrocyclic ligand plane is parallel to the a axes, and the normal to the plane is inclined at 62.6 ° to the b axes and 27.8 ° to the z axes. The mutual arrangement of molecules and stereopacking in unit cell is shown in Fig. 2. The angle between two neighbouring phthalocyanine planes is 54.7 °. The perpendicular distance between successive planes is equal to 4.42 ~. The broken lines in Fig. 2 represent a very weak interaction between T1 and the nitrogen atom with the neighbouring molecule. This distance, T1-N(3), between two molecules of phthalocyanine is equal to about 3.516 ~. Recently we found that the orthorhombic TlzPc exhibits a reversible phase transition somewhere under 280 K. The low temperature modification is probably monoclinic. The analysis of that transition is in progress and the results will be published later. 4. S u p p l e m e n t a r y material Lists of observed and calculated structure factors and anisotropic thermal parameters, as well as other details and the molecular geometry, are available from the present authors on request. Acknowledgment The authors are grateful to Professor Z. Ga/decki from the Technical University of L6d~, Poland, for the opportunity to perform calculations (SrmLX'rL program system) in his laboratory. References 1 J.R. Ferraro and J.M. Williams, Introduction to Synthetic Electrical Conductors, Academic Press, Orlando, FL, 1987, p. 219. 72 Z Janczak, R. Kubiak / Crystalline dithallium phthalocyanine 2 M.Y. Opawa, J. Martinsen, S.M. Palmer, J.L. Stanton, J. Tanaka, R.L. Greene, B.M. Hoffman and J.A. Ibers, J. Am. 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