Iron(I1) and Manganese(I1) Phthalocyanines tetrahedrally coordinated Fe. The Mossbauer shift for octahedral Fez+appears to be 0.90 mm/s. Knowledge of isomer shifts for the compounds Fe[SzCN(n-Bu)z] 3 and Fe[S2CN(CH2)4]3, in which iron atoms are in the trivalent oxidation state, would be extremely valuable in order to establish its variation with valence in octahedrally coordinated iron compounds.
AcknowledgmenC Financial support for this research effort by the National Science Foundation and the Robert A. Welch Foundation, Houston, Tex., is gratefully acknowledged. The comments of Dr. R. D. Shannon have been very helpful in the preparation of this manuscript, and we wish to thank him also for communicating to us his results on FezSiS4 and Fe2GeS4 prior to their publication. Registry No. Ba&es&s, 37204-48-1; BazFeS3, 37204-45-8; BaFe&,37204-43-6; Ba7Fe&, 12537-50-7; Ba3FeS5,589 15-68-7; BalsFe7Szs,58915-69-8;BasFegSl8, 53810-48-3; CuFe&, 1308-56-1; CuzFeSnS4, 12019-29-3; CuFezS3, 12140-08-8; KFeS2, 12022-42-3; RbFeSz, 12140-50-0; CsFeSz, 12158-53-1; NaFeSz, 12160-05-3; FeCrzS4, 12018-1 2-1; FeInzS4, 12292-75-0; FezSiS4, 591 23-33-0; FezGeS4, 12332-32-0; Fe7S.8, 12063-67-1; FeS, 1317-37-9; Fe& 36841-25-5; (n12063-38-6; [(n-Bu)4N]z[FeS~(CH2)2]2, Bu)4NFe[SzC2(CN)2]2, 31358-28-8; [Ph4As]zFe[SzCz(CN)z]3, 25595-40-8; Fe[SzCN(n-Bu)z]3, 14526-32-0; Fe[SzCN(CH2)4]3, 21288-86-8; Fe([SP(CH3)z]zN)2, 29950-57-0; [Ph4As]zFe4S4[S2Cz(CF3)2]4, 12572-53-1; (EtqN)2[Fe&4(SCH2Ph)4], 50923-41-6.
References and Notes (1) I. E. Grey, H. Hong, and H. Steinfink, Inorg. Chem., 10, 340 (1971). (2) H. Hong, I. E. Grey, and H. Steinfink, Natl. Bur. Stand. (U.S.), Spec. Publ., No. 364 (1972). (3) H. Hong and H. Steinfink, J . Solid State Chem. 5, 93 (1972). (4) W. M. Reiff, I. E. Grey, A. Fan, Z Eliezer, and H. Steinfink, J . Solid State Chem., 13, 32 (i975). J. T. Lemley, J. M. Jenks, J. T. Hoggins, Z . Eliezer, and H. Steinfink, J . Solid State Chem., 16, 117 (1976). M. B. Robin and P. Day, Adu. Inorg. Chem. Radiochem. 10,247 (1967). I. D. Brown and R. D. Shannon, Acta Crystallogr.,Sect. A, 29,266 (1973). R. W. G. Wyckoff, “Crystal Structures”, Why-Interscience, New York, N. Y., 1963. A. Davidson and E. S. Switkes, Inorg. Chem., 10, 837 (1971).
Inorganic Chemistry, Vol. IS, No. 7, 1976 1685 V. W. Bronger, Z . Anorg. Allg. Chem., 359, 225 (1968). S. R. Hall and J. M. Stewart, Acta Crystallogr.,Sect. B, 29,579 (1973). N. E. Erickson, Adu. Chem. Ser., No. 68, 86 (1967). P. C. Healy and A. H. White, Chem. Commun., 1446 (1971). J. Danon, “Chemical Applications of Mossbauer Spectroscopy”, V. I. Gol’danskii and R. H. Herber, Ed., Academic Press, New York, N. Y., 1963, Chapter 3. J. G. Norman, Jr., and S. C. Jackels, J. Am. Chem. Soc., 97,3833 (1975). J. G. Norman, Jr., private communication. T. Teranishi, J . Phys. SOC.Jpn., 16, 1881 (1961). E. F. Bertaut, P. Burlet, and J. Chappert, Solid State Commun., 3, 335 (1965). D. J. Vaughan and M. S. Ridout, J. Inorg. Nucl. Chem.,33,741 (1971). I. E. Grey, Acta Crystallogr., Sect. B, 31, 45 (1975). S. Takeno, K. Masumoto, and T. Kamigaichi, J. Sci. Hiroshima Uniu., Ser. C, 5, 341 (1968). L. 0. Brockway, Z . Kristallogr., Kristallgeom., Kristallphys., Kristallchem., 89, 434 (1934). M. E. Fleet, Z . Kristallogr., Kristallgeom.,Kristallphys., Kristallchem., 132, 276 (1970). D. Raj and S. P. Puri, J . Chem. Phys., 50, 3184 (1969). D. 0. Cowan, G. Pasternak, and F. Kaufman, Proc. Natl. Acad. Sci. U.S.A.,66, 843 (1970). M. R. Spender and A. H. Morrish, Can. J . Phys., 50, 1125 (1972). H. Hahn and W. Klinger, 2. Anorg. Allg. Chem., 263, 177 (1950). H. Vincent, E. F. Bertaut, W. H. Baur, and R. D. Shannon, to be submitted for publication. R. D. Shannon, private communication. M. Tokonami, K.Nishiguchi, and N. Morimoto, Am. Mineral., 57,1066 (1972). D. J. Vaughan and M. S. Ridout, Solid State Commun.,8,2165 (1970). M. E. Fleet, Acta Crystallogr., Sect. B, 27, 1864 (1971). H. T. Evans, Jr., Science, 167, 621 (1970). A. F. Andresen, Acta Chem. Scand., 14, 919 (1960). S. Hafner and M. Kalvius, 2.Kristallogr., Kristallgeom., Kristallphys., Kristallchern., 123, 443 (1966). B. J. Skinner,R. C. Erd, and F. S. Grimaldi,Am. Mineral.,49, 543 (1964). J. M. D. Coey, M. R. Spender, and A. H. Morrish, Solidstate Commun., 8, 1605 (1970). M. R. Snow and J. A. Ibers, Inorg. Chem., 12, 249 (1973). W. C. Hamilton and I. Bernal, Inorg. Chem., 6, 2003 (1967). N. N. Greenwood and H. J. Whitfield, J . Chem. Sot. A , 1697 (1968). A. Sequeira and I. Bernal, J . Cryst. Mol. Strucr., 3, 157 (1973). B. F. Hoskins and B. P. Kelly, Chem. Commun., 1517 (1968). P. C. Healy and A:H. White, J . Chem. Soc. A, 1163 (1972). M. R. Churchill and J. Wormald, Inorg. Chem., 10, 1778 (1971). I. Bernal, B. R. Davis, M. L.Good, and S. Chandra, J . Coord. Chem., 2, 61 (1972). T. Herskovitz, B. A. Averill, R. H. Holm, J. A. Ibers, W. D. Phillips, and J. F. Weiker, Proc. Natl. Acad. Sci. U.S.A., 69, 2437 (1972).
Contribution from the Department of Chemistry, University of Notre Dame, Notre Dame, Indiana 46556
Molecular Stereochemistry of Two Intermediate-Spin Complexes. Iron(11) Phthalocyanine and Manganese(I1) Phthalocyanine J O H N F. KIRNER, W. DOW, and W. ROBERT SCHEIDT’ Received January 15, 1976
AIC600426
The molecular stereochemistry of iron(I1) phthalocyanine and manganese(I1) phthalocyanine has been determined by x-ray diffraction methods. The phthalocyanine ligand constrains the metal ion to effectively square-planar coordination and to an intermediate spin state. The FeII-N bond distance of 1.926 (1) 8, and the MnII-N bond length of 1.938 (3) 8, are wholly consistent with the assignment of an intermediate-spin ground state. Both complexes crystallize as the /3 polymorph, Crystal data are as follows: for FePc, space group P21/a, a = 19.392 (5) A, b = 4.786 (2) 8,, c = 14.604 (4) A, p = 120.85 (l)’, pexptl = 1.61 g/cm3, pcal& = 1.623 g/cm3 for 2 = 2, required molecular symmetry I; for MnPc, space group P21/a, a = 19.400 (4) A, b = 4.761 (2) A, c = 14.613 (3) A, /3 = 120.74 (l)’, pexptl= 1.61 g/cm3, pcalcd = 1.625 g/cm3 for Z = 2, required molecular symmetry i. Intensity data were measured by 8-20 scanning on a Syntex P1 automated diffractometer using graphite-monochromated Mo K a radiation. For FePc, the intensities of 3949 reflections with (sin $)/A 5 0.817 A-1 were used in the refinement of the 187 structural parameters and for MnPc the intensities of 2158 reflections having (sin $)/A C 0.69 8,-’ were employed. Final discrepancy indices are as follows: FePc, R1 = 0.045, R2 = 0.057; MnPc, R1 = 0.066, Rz = 0.066.
Iron( 11) and manganese( 11) phthalocyanine have been recognized as examples of a rare type of coordination compound in which the metal ion has an intermediate-spin ground state (Fe, S = 1; Mn, S = 3/2).1 The basic stereochemistry
of four-coordinate phthalocyanines has been known for some time,2,3 but surprisingly the quantitative stereochemistry of the much studied iron(I1) and manganese(I1) derivatives has not been determined. We report herein the structures of
1686 Inorganic Chemistry, Vol. 15, No. 7, 1976 Table I. Summary of Crystal Data and Intensity Collection Compd a, A
b, A C,
P , deg
v,A3
Z
Density, g/cm3 Space group Crystal dimensions, mm Temp, "C Radiation
mm-' Scan range
p,
MnN8C32
16
FeN8C32H16
19.400 (4) 4.761 (2) 14.613 (3) 120.74 (1) 1160.0 2 1.625 (calcd) 1.61 (obsd) P2,la 0.77 X 0.13 X 0.10
19.392 (5) 4.786 (2) 14.604 (4) 120.85 (1) 1163.7 2 1.623 (calcd) 1.61 (obsd) P2,la 0.90 X 0.33 X 0.30
20 f 1 Graphite-monochromated Mo Ka ( h 0.710 69 A) 0.586 0.8" below KO, to 1.O" above K a , Profile analysis 3.5-58.7 2158
20 i: 1 Graphite-monochromated Mo K a (h 0.710 69
Kirner, Dow, and Scheidt Table 11. Atom Coordinates in the FePc Unit Cella Atom
104x
104y
10%
Fe Nl N*
0 -788 (1) 327 (1) 1601 (1) 969 (1) -97 (1) 321 (1) 130 (1) 664 (1) 1363 (1) 1556 (1) 1017 (1) 1014 (1) 1574 (1) 2209 (1) 2950 (1) 3426 (1) 3179 (1) 2443 (1) 1965 (1) 1189 (1)
0 -5159 (3) -1953 (3) 279 (3) 2187 (3) -4053 (4) -4953 (4) -6957 (4) -7269 (5) -5677 (5) -3687 (4) -3357 (4) -1506 (3) 1964 (3) 3935 (4) 4506 (4) 6532 (5) 7960 (4) 7407 (4) 5365 (3) 4248 (3)
0 724 (1) 1315 (1) 2519 (1) 729 (1) 1449 (1) 2552 (1) 3081 (1) 4166 (2) 4706 (2) 4173 (1) 3084 (1) 2292 (1) 1785 (1) 2002 (1) 2917 (1) 2833 (2) 1882 (2) 972 (1) 1053 (1) 273 (1)
N3
N4
c, c3 c, c 2
c5
Backgrounds 26 limits, deg Unique data used, Fa > 30(Fa) Final no. of variables 187
a)
0.688 1.OD balow Ka, to 1.O" above K a , Profile analysis 3.5-71" 3949 187
MnPc4and FePc and compare them with the recently reported structures of the related four-coordinate iron(II)S and manganese(II)6 metalloporphyrins. Differences in structure between intermediate-spin MnPc, FePc, and FeTPP and high-spin MnTPP are wholly consistent with the assigned ground states of the complexes.
C6
c, C8 c 9
ClO Cll Cl1 1'
3
1 '
5
c,, C16
a The figure in parentheses following each datum is the estimated standard deviation in the last significant figure.
-3
3
Experimental Section FePc7 and MnPc* were prepared by published procedures and purified by vacuum sublimation. Single crystals, suitable for diffraction analysis, were grown by vacuum sublimation in quartz tubes at -450 "C under a nitrogen atmosphere (reduced pressure). Crystals used in the structure analysis were cut from larger needles. Some difficulty was experienced in obtaining satisfactory crystals of MnPc. Preliminary photographic examination by Weissenberg photography, Cu K a radiation, showed that MnPc and FePc crystallized as the monoclinic /3 polymorph. The space group P21/a [C2h5,No. 141: a nonstandard choice, was chosen to conform with earlier choices of the unit cells of four-coordinate phthalocyanine^.^ Lattice constants (Table I) came from a least-squares refinement that utilized the setting angles of 30 reflections (FePc) or 60 reflections (MnPc) giv_enby the automatic centering routine supplied with the Syntex P1 diffractometer. X-ray intensity data were collected using graphite-monochromated Mo Ka radiation on a computer-controlled four-circle diffractometer, using 8-28 scanning, to the 20 limits listed in Table I. Background counts were estimated from an analysis of the reflection profiles using a local modification of a program recently described.I0 Four standard reflections, measured every 50 reflections during data collection, showed no trend with exposure to the x-ray beam. Although the linear absorption coefficients (Table I) are not large, an empirical absorption correction was applied to the data." Intensity data were reduced and standard deviations were calculated as described previously.12 Data were retained as objectively observed if Fo > 30(F0), leading to 2158 unique observed data for MnPc (68% of the theoretical number possible) and 3949 unique data for FePc (74% of theoretical). Atomic coordinates reported for CuPc13 were used for the initial coordinates in the asymmetric unit of structure (half of the MPc molecule). Full-matrix least-squares refinement14converged smoothly using isotropic temperature factors for all atoms and standard ~ a l u e s ' ~for ~ ~atomic 6 form factors. Difference Fourier syntheses17 gave electron density concentrations appropriately located for all hydrogen atom positions; these positions were idealized (C-H = 0.95 A) with temperature factors fixed one unit higher than those of the associated carbon atoms. Subsequent refinements used anisotropic temperature factors for all heavy atoms and fixed hydrogen contributors and were carried to convergence. For both complexes, the final parameter shifts were less than 10% of the estimated standard deviation during the last cycle. For FePc, the final value of R1 =
Figure 1. Computer-drawn model in perspective of the centrosymmetric FePc molecule as it exists in the crystal. On the lower half of the diagram the special symbol identifying each atom is shown. On the upper half of the figure, the symbol for each atom is replaced by its perpendicular displacement, in units of 0.01 A, from the mean plane of the entire molecule.
CIIFol- IFcll/CIFolwas
0.045; that of R2 = [C:w(lFol.Cw(FO2)l1/*was 0.057. The estimated standard deviation of an observation of unit weight was 1.37, with a final data:parameter ratio of 21.1. A final difference Fourier had no significant features; the largest peaks were
