1530 Inorganic Chemistry, Vol. 16, No. 6, 1977
Baker et al.
Contribution from the Departments of Chemistry and Physics, University of Texas at Arlington, Arlington, Texas 76019, and the Department of Chemistry, Texas Christian University, Fort Worth, Texas 76129
Synthesis, Magnetism, Electron Paramagnetic Resonance Studies, X-Ray Molecular Structure, and Spectral Properties of p4-Oxo-hexa-~-chlorotetrakis[(3-quinuclidinone)copper(11)] RICHARD C. DICKINSON, FRED T. HELM, W. A. BAKER, Jr.,* T. D. BLACK, and W . H . WATSON, Jr. Received Nouember 23, 1976 AIC60849Y The title compound, which has been characterized by a single-crystal x-ray diffraction study, is shown to be a p4-oxo-bridged cluster compound of the general type [Cu40X,,,L,] n-4. It crystallizes as orange pinacoidal crystals in the centric, monoclinic space group P2'/c with a = 11.877 (4) A, 6 = 19.106 (3) A, c = 21.975 (5) A, p = 122.28 (2)', V = 4328 A3, and 2 = 4. Single-crystal x-ray diffraction data, complete to 28 = 50' (Mo K a radiation), were collected on a Syntex P2, automatic diffractometer, and the structure was solved by a combination of Patterson, Fourier, and least-squares refinement techniques. Final discrepancy values of R = 6.9% and R, = 7.0% were obtained for 4798 independent reflections and 304 adjustable parameters. The molecule consists of a central oxide ion coordinated tetrahedrally to four copper(I1) ions; the copper(I1) ions are bridged in pairs by six chloride ions which comprise a fairly regular octahedron around the central oxide ion, O( 1). A total of four molecules of 3-quinuclidinone (3-quin) complete the trigonal-bipyramidal coordination sphere around each copper(I1) ion. The C ~ ~ O C I ~ ( 3 - q umolecule i n ) ~ does not have rigorous Td symmetry nor does the central oxide ion occupy any special crystallographic symmetry site in the unit cell. Nevertheless, a nearly perfect tetrahedron of copper(I1) ions is observed around O( I ) . Some pertinent interatomic distances and angles are Cu-O(1) = 1.915-1.925 8, (average 1.919 f 0.005 A), Cu-O(1)-Cu = 108.9-110.3° (average 109.5 f 0.5'), Cu-Cu = 3.120-3.155 A (average 3.134 f 0.013 A), O(l)-Cl = 2.932-2.956 8, (average 2.946 3~ 0.009 A), CI-CI = 4.093-4.232 8, (average 4.161 f 0.044 A), CI-O(1)-CI = 88.2-91.9' (average 90.0 f 1.3'), N-Cu-C1 = 94.5-96.3' (average 95.3 f 0.6'), and O(1)-Cu-CI = 83.9-85.9' (average 84.8 f 0.5'). The existence of two distinct types of axial-equatorial angles about each copper-namely, N-Cu-CI and O(1)-Cu-CI-is witness to the fact that each copper(I1) ion is displaced (in the direction of the nitrogen atom of 3quinuclidinone) approximately 0.2 A out of the equatorial plane of the three coordinated chloride ions. Magnetic susceptibility measurements in the temperature range 302.9-1.27 K revealed a ferromagnetic interaction between the four metal ions of the cluster to temperatures of ca. 20 K; below 20 K, the values of peffrapidly decreased with decreasing temperature, The magnetic susceptibility per copper ion was fit to a modified Heisenberg model which included, in addition to the usual g factor and intramolecular exchange integral, an intermolecular exchange parameter, z'J'. The computed "best fit" for these parameters was g = 2.178 f 0.010 cm-', J = 47.34 f 2.15 cm-', and z'J'= -0.316 f 0.018 cm-', respectively. The low-temperature EPR spectra of powdered samples of this compound confirmed the g value and the ferromagnetic nature of the intramolecular exchange coupling. Chemical Co.) dissolved in 50 mL of dry, boiling methanol was mixed Introduction with 1.05 g of CuC12.2H20 (6.2 mmol) also dissolved in 50 mL of Our research into the relationship between magnetic dry, boiling methanol. A solution composed of 0.50 g of sodium properties and molecular structure has recently concentrated methoxide (9.3 mmol) in 50 mL of hot methanol was added dropwise on magnetic exchange interactions in multinuclear transition to this mixture. The reaction mixture gradually darkened, and a metal complexes. Of particular interest have been tetranuclear brown-orange solid formed; heating was continued for ca. 15 min after complexes of copper(I1) which have the general stoichiometry addition of NaOCH,. After cooling to ambient temperature, the product was collected by filtration, washed with methanol, and dried [ C U ~ O X , ~ - ~ Lwhere , ] " ~ ~X represents a chloride or bromide in vacuo over P4Ol0overnight. ion and L represents a Lewis base ligand. These complexes Recrystallization of the crude product from warm benzene gave contain both p4-bridging oxygen and p-bridging halogens a benzene solvate, CU@c&( 3-qUin)4*0.75C6H6. Anal. Calcd for between the copper ions. C~4C325Ha5Nj05C16:CU,24.39; C, 37.46; H, 4.69; N, 5.38; CI, 20.41. The first account of such complexes was a preliminary report Found: Cu, 24.67; C, 37.29; H, 5.05; N , 5.30; C1, 20.55. on C U ~ O C ~ ~ ( P and ~ ~ [(CH3)4N]4[C~40C110] PO)~ given by Recrystallization of the crude product from warm toluene gave a Bertrand and Kelley.' It was Lines, Ginsberg, Martin, and toluene solvate, Cu40C16(3-quin)4.0.75CH3C6H5. Anal. Calcd for Sherwood" who reported the unusual magnetic properties of C U ~ C ~ ~ ~ ~ H S OCU, N ~24.15; O ~ CC,I ~37.94; : H, 4.79; N, 5.32; C1, 20.21. the compounds. They found that for C U ~ O C ~ ~ ( P ~peff ~ P O ) Found: ~, Cu, 23.76; C, 37.47; H, 4.66; N, 5.20; CI, 19.99. Crystals large enough for use in the collection of x-ray diffraction increased to a maximum at temperatures in the range 40-60 data were not obtained readily by recrystallization from either benzene K; below these temperatures the values of perfrapidly deor toluene. A few sizable, well-formed crystals were obtained by creased. On the contrary, the values of M e f f for [(CH3)4recrystallization of the toluene solvate from a chloroform-ethyl acetate NI4[Cu40Cll0]steadily decrease with decreasing temperature. mixture, and one of these crystals was selected for use in the data To date, numerous other accounts of such compounds have collection. The solvent content of these crystals was difficult to been r e p ~ r t e d * - ' ~ ~but ' ~ -few ' ~ detailed magnetic investigations determine crystallographically because of disorder; however, the have been reported. We have prepared a tetramer of formula structural parameters for C ~ ~ O C I ~ ( 3 - q ucould i n ) ~be ascertained. The Cu40Cl6(3 - q ~ i n containing )~ both stoichiometric and nonrecrystallized products appeared brownish yellow by reflected light; stoichiometric amounts of solvent. We have studied the microscopic examination showed them to be microcrystalline needles, magnetism, spectral properties, and electron paramagnetic yellow by transmitted light. Collection and Treatment of X-Ray Diffraction Data. The crystal resonance spectra of the stoichiometric toluene solvate and chosen for data collection was an abbreviated pinacoid, the growth determined the crystal and molecular structure of the nonof one of the faces having been inhibited by contact with the solvent stoichiometric solvate.
Experimental Section Preparation of C ~ ~ O C l ~ ( 3 - q u i nA) ~1.OO-g . sample of 3-quinuclidinone hydrochloride (6.2 mmol, used as received from Aldrich To whom correspondence should be addressed at the Department of Chemistry, University of Texas at Arlington.
vessel. Maximum crystal dimensions in three orthogonal directions were 0.50 mm X 0.33 mm X 0.18 mm. The unit cell was found to be monoclinic and room-temperature cell dimensions were obtained from a least-squares fit of 15 reflections, centered by the half-height technique on a Syntex P2' automated four-circle diffractometer. Crystal data: C ~ ~ C ~ ~ H ~ ~ N ~ O ~ C a l=~11.877 ~solv (4)e nA,t ,6 = 19.106 (3) A, c = 21.975 (5) A, = 122.28 (2)O, V = 4238 A3, Z
Studies on C ~ ~ O C l ~ ( 3 - q u i n ) ~
Inorganic Chemistry, Vol. 16, No. 6, 1977 1531
= 4, d,,,,d(flotation in aqueous CdClJ = 1.70 (1) g ~ m - dcalcd(for ~, toluene solvate) = 1.69 g ~ m - p~ = , 24.95 cm-l; space group P2,/c from systematic absences h01 when 1 = 2n 1 and OkO when k = 2n 1. Intensity data with 4O I28 I 50° were collected on the Syntex P2, diffractometer by the 28% mode using graphite-monochromatized Mo K a radiation (A 0.71069 A) and a variable scan rate (7.3229.30°/min). The intensities of three reflections were monitored and no significant crystal deterioration was observed. Of the more than 8000 independent reflections measured, 4798 had intensities greater than 2 4 1 ) where the net intensity I and its estimated standard deviation were calculated from I = S(P - B1 - Bz) and .’(I) = S(P B I Bz). Lorentz, polarization, and absorption corrections were applied. Transmission factors (0.5 11 I T F 5 0.754) were calculated using a version of Busing’s Fortran IV program ORABS, the accuracy of which was verified with the test data of A1cock.28 Determination and Refinement of the Structure. The scattering factors of Cromer and Waber2’ for neutral copper, chlorine, oxygen, nitrogen, and carbon were used without further correction. The function minimized during least-squares refinement processes was xw(lFol - IFc1)2,where w = l / u 2 and uz = &I) (0.021)’. Discrepancy factors are defined by R = [ ~ y F , , I -IFcll/CIFol]X 100 (96) and R, = [xw(lFol - IFcl)2/~wlFoI 1’’ X 100 (%). All calculations were carried out on the Xerox SIGMA9 computer at Texas Christian University. In addition to various locally written programs, Zalkin’s FORD- Fourier summation program, Okaya’s block-diagonal least-squares and distanceangle programs, Ibers’ NUCLS modification of the Busing-Martin-Levy ORFW full-matrix least-squares program, and Johnson’s ORTEP plotting program were used. Atomic coordinates for the four independent copper atoms were deduced from a three-dimensional Patterson synthesis and were refined by least-squares techniques. The chlorine, oxygen, nitrogen, and carbon atoms were located by means of subsequent difference Fourier syntheses. Toward the completion of the structure determination (R = 11%) not all the atoms indicated in the formula for the toluene solvate could be located in the difference maps. The oxygen atoms of three 3-quinuclidinone ligands show a twofold disorder. The quinuclidinone coordinated to Cu( 3) exhibits an approximate 50% occupancy for the two oxygen sites. Carbon C( 18) which is attached to oxygen O(6) also is disordered. The carbon occupies one site when the oxygen O(6) is present and another site, C(19), when the oxygen occupies the O(5) site. This mirror or partial rotational disorder probably is associated with solvent and packing interactions. Detailed interpretations of these interactions is complicated by the disorder of the solvent molecules in the large cavities between the complexes. During recrystallization toluene molecules have been partially or entirely replaced by chloroform, ethyl acetate, or fragments of its hydrolysis. Positions for the solvate atoms were obtained from difference Fourier maps and were 1.3-3.4 e in magnitude. These peaks could not be associated with any particular model for a solvent molecule. Initially the coordinates and occupancy factors for these solvate atoms were refined employing fixed isotropic temperature factors ( B = 6.0 A’) and carbon scattering factors, but toward the completion of least-squares refinement, the occupancy factors were fixed at their refined values and the temperature factors were allowed to vary. N o attempt was made to locate hydrogen atoms. Full-matrix and block-diagonal least-squares techniques were used in the final stages of refinement. Anisotropic temperature factors were applied to the central oxygen atom and the four copper and six chlorine atoms, and isotropic temperatures were applied to the remaining atoms. With 62 atoms (51 isotropic and 11 anisotropic), 304 parameters, and 4798 observables, the final discrepancy factors were R = 6.9% and R, = 7.0%, with a standard deviation of 0.865 for observations of unit weight. Observed and calculated structure factors are available as supplementary material. Final atomic positional and isotropic thermal parameters are listed in Table I; anisotropic thermal parameters are given in Table 11. Physical Measurements. Magnetic susceptibility data in the temperature range -300--25 K were collected using a Faraday balance as previously described.” Magnetic susceptibility data at temperatures below 35 K were obtained by the Faraday method using a Cahn R G electrobalance and a Janis Varitemp cryostat. An SiOz sensor was used to measure temperatures above 30 K, a GaAs sensor was used for temperatures below 30 K, and the vapor pressure of helium was used to determine temperatures below 4.2 K. Temperature
+
+
X‘4 04
03
+ +
+
Figure 1. Overall stereochemistry of one molecule of Cu40Cl6(3The atoms O(3) and 0 ( 4 ) , O(5) and 0 ( 6 ) , O(7) and 0(8), and C ( 18) and C ( 19) represent approximate twofold disordered positions in the three 3-quinuclidinone ligands. control was f0.001 to 10.01 K for temperatures greater than 4.2 K and fO.OO1 K or better for lower temperatures. Electron paramagnetic resonance studies were made using a basic ku-band homodyne spectrometer configuration with a low-noise back-diode detector system. The microwave source, a Varian X-12 klystron, was frequency-stabilized to the sample cavity to ensure sensitivity to the resonant absorption. A powdered, microcrystalline sample was packed into a spectroscopic grade quartz tube and inserted into the center of the spectrometer cavity turned to ca. 13.5 G H z for the TEIo2mode. A reference sample of DPPH (2,2-diphenyl-lpicrylhydrazyl) was placed in the bottom of the cavity. A Varian V-3900 12-in. Mack I Fieldial magnet provided the resonant magnetic field as well as a linear scanning field with a precise x-axis output. A cryogenic Dewar system provided stable temperatures of 77 and 4.2 K. Precise laboratory g values were determined by simultaneously measuring the resonant microwave frequency and the resonant N M R frequency of a sample of HzO at the EPR magnetic field. Both the N M R frequency and the EPR frequency were calibrated with reference to the same crystal-controlled time base. The EPR spectrometer was interfaced with a two-channel analog-to-digital convertor which allowed accurate numerical analysis of the line shape of the resonant absorption. Electronic absorption spectra were obtained using a Cary 14 spectrophotometer by emulsifying the solid in a fluorocarbon grease and mounting the emulsion between two thin quartz plates; spectra of solutions were obtained using matched quartz cells. Infrared spectra in the range 4000-200 cm-’ were recorded on a Perkin-Elmer 621 spectrophotometer; the samples were prepared by grinding the copper complex with KBr or CsI and pressing the resulting powders into thin disks. Elemental analyses were performed by Galbraith Laboratories, Inc., Knoxville, Tenn.
Results and Discussion X-Ray Molecular Structure. The geometry of the C ~ ~ O C l ~ ( 3 - q umolecule i n ) ~ is shown in Figure 1 along with the labeling system used in the discussion. Interatomic distances, with their estimated standard deviations (esd’s), are collected in Table 111; bond angles, with esd’s, are given in Table IV. The molecule consists of a tetrahedron of copper(I1) ions held together by one central p4-bridging oxide ion and six p-bridging chloride ions; a 3-quinuclidinone molecule is bound to each copper ion via nitrogen in a terminal fashion. The Cu40 tetrahedron is approximately regular, although perfect Td symmetry is neither achieved nor required by crystallographic site symmetry; the central oxygen atom occupies a
1532 Inorganic Chemistry, Vol. 16, No. 6, 1977
Baker et al.
Table I. Final Positional and Isotropic Thermal Parameters for Cu,OCI, (3-quin),*~(solvate)~ Atom
x
Y
Z
0.014 14 (11) 0.001 33 (11) -0.161 76 (10) 0.149 25 (10) 0.219 27 (25) -0.189 74 (27) 0.014 94 (33) 0.197 78 (26) -0.220 35 (23) -0.013 87 (20) 0.028 9 (7) 0.002 7 (7) -0.330 6 (7) 0.307 7 (7) 0.000 2 (5) -0.178 0 (10) -0.208 l ( 1 3 ) 0.242 3 (41) -0.484 4 (30) -0.512 5 (35) 0.407 0 (37) 0.664 2 (12) -0.574 l ( 8 ) -0.427 7 (9) -0.374 0 (11) -0.090 3 (11) -0.081 5 (11) 0.047 4 (11) 0.157 4 (12) 0.154 2 (11) 0.032 8 (10) 0.055 4 (12) -0.112 6 (11) -0.110 8 (12) -0.001 2 (11) 0.128 9 (14) 0.130 5 (11) -0.118 (10) -0.012 l(11) -0.324 8 (11) -0.452 2 (16) -0.546 6 (12) -0.456 9 (34) -0.479 3 (19) -0.345 9 (1 1) -0.449 9 (11) -0.579 9 (13) 0.301 7 (10) 0.425 7 (12) 0.513 4 (11) 0.552 3 (11) 0.434 5 (10) 0.309 8 (10) 0.428 9 (12) -0.527 8 (26) -0.336 8 (23) -0.416 5 (39) -0.514 4 (31) -0.496 6 (37) -0.531 4 (32) -0.583 l ( 4 4 ) -0.394 7 (39)
0.032 08 (6) 0.195 0 1 (6) 0.114 92 (6) 0.122 66 (6) 0.014 24 (14) -0.000 74 (14) 0.107 15 (14) 0.229 23 (14) 0.215 94 (14) 0.122 5 3 (14) -0.057 3 (4) 0.277 9 (4) 0.114 1 (4) 0.129 5 (4) 0.116 2 (3) -0.164 l ( 5 ) 0.340 6 (8) 0.373 6 (23) -0.006 9 (15) 0.235 9 (20) 0.231 5 (20) 0.117 2 (7) 0.375 5 (4) 0.305 5 (5) 0.453 1 (6) -0.067 9 (6) -0.138 5 (6) -0.175 9 (6) -0.125 7 (6) -0.058 1 (6) -0.1 18 4 (6) -0.189 6 (6) 0.272 7 (6) 0.336 2 (6) 0.385 9 (6) 0.343 5 (8) 0.280 7 (6) 0.345 4 (5) 0.410 6 (6) 0.054 4 (6) 0.056 0 (8) 0.111 8 (7) 0.167 l ( l 9 ) 0.181 2 (11) 0.180 9 (6) 0.102 8 (6) 0.101 l ( 7 ) 0.196 2 (5) 0.202 2 (6) 0.138 0 (6) 0.131 7 (6) 0.129 2 (5) 0.068 3 (5) 0.072 1 (6) 0.385 2 (15) 0.419 5 (13) 0.374 7 (21) 0.353 6 (18) 0.402 1 (19) 0.407 l ( 1 7 ) 0.353 3 (24) 0.456 l ( 2 1 )
0.193 34 (6) 0.182 39 (6) 0.236 34 (5) 0.333 41 (5) 0.308 33 (14) 0.185 71 (17) 0.106 37 (15) 0.292 89 (14) 0.159 31 (14) 0.365 86 (11) 0.148 9 (4) 0.125 6 (4) 0.238 5 (4) 0.435 7 (4) 0.236 2 (3) -0.006 5 (5) -0.057 7 (7) 0.109 5 (22) 0.291 8 (15) 0.269 7 (18) 0.590 6 (20) 0.525 7 (6) 0.475 0 (4) 0.425 4 (5) 0.452 4 (6) 0.074 4 (6) 0.046 3 (6) 0.094 0 (6) 0.106 9 (6) 0.146 6 (6) 0.193 4 (6) 0.166 1 (6) 0.048 8 (6) 0.006 8 (6) 0.051 0 (6) 0.081 9 (7) 0.126 5 (6) 0.157 5 (5) 0.1 14 9 (6) 0.285 2 (6) 0.287 8 (8) 0.241 6 (7) 0.292 7 (20) 0.260 3 (12) 0.267 5 (6) 0.163 2 (6) 0.164 5 (7) 0.470 9 (5) 0.549 2 (6) 0.567 4 (6) 0.513 7 (6) 0.436 3 (5) 0.479 7 (5) 0.557 7 (6) 0.333 l ( 1 5 ) 0.496 8 (12) 0.479 9 (21) 0.372 6 (18) 0.432 3 (20) 0.489 0 (18) 0.447 8 (24) 0.484 4 (22)
B, A2
3.24 3.35 3.30 2.89
(14) (14) (13) (13)
7.62 (22) 7.46 (31) 10.4 (11) 13.94 (78) 11.79 (89) 6.90 (82) 6.81 (26) 6.10 (18) 6.89 (20) 7.92 (25) 4.46 (21) 4.80 (23) 5.09 (24) 5.52 (25) 4.50 (21) 4.33 (19) 5.29 (24) 4.48 (21) 5.12 (23) 5.21 (23) 6.76 (31) 4.41 (21) 3.93 (19) 4.73 (22) 4.57 (22) 7.62 (35) 5.90 (26) 5.98 (76) 4.11 (38) 4.64 (22) 4.62 (22) 6.41 (19) 4.14 (20) 5.34 (25) 4.56 (22) 4.97 (23) 4.19 (20) 3.78 (19) 5.38 (25) 8.02 (57) 6.38 (45) 7.55 (83) 8.75 (76) 7.25 (79) 5.76 (70) 6.67 (95) 5.70 (78)
a All atoms are at full occupancy unless indicated otherwise. Atoms O(3) and 0(4), O(5) and 0(6), and O(7) and O(8) correspond to disordered positions for the quinuclidinone oxygens. Atoms C(30)
