4425
Inorg. Chem. 1989, 28, 4425-4427 availability of excited states t h a t respectively lead to angular (ligand field) and radial (charge transfer) reorganizations of the electronic density with respect to the ground state can justify, therefore, the observed photochemical properties of the Mo(V) dimers. Acknowledgment. The research described herein was supported by t h e Office of Basic Energy Sciences of t h e Department of Energy.
Contribution from the Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309
Two Polymorphs of the Diazaphosphole Oxide
CJWJH)$'(O)Ph Joseph M. Barendt, Elizabeth G. Bent, R. Curtis'Haltiwanger, Christopher A. Squier, and Arlan D. Norman*
Received May 1 , 1989
Our investigations of skeletally stabilized P(II1) phosphazane ~ ~ stimulated studies of P(II1) and oligomers/polymers ( 1 ) ' have P ( V) 1,3-dihydro- 1,3,2-diazaphospholes, especially the P-phenyl derivatives 2 (R = P h ) and 3. Pilgram and Korte' claimed the
Table I. Crystal Data, Data Collection Parameters, and Refinement Details for C6H4(NH)2P(0)Ph (3A and 3B) 3A 3B formula fw space group a, A
b, A
c, A v , A3 Z A, A dcalog cm-' F(OO0) temp, OC p, cm-'
R Rw
C12HIIN2OP 230.20 Pnma 17.816 (4) 7.578 (2) 8.709 (2) 1175.9 (4) 4 1.541 78 (Cu Ka) 1.30 480 22-24 19.1 0.036 0.05 1 I
C12HllN20P 230.20 Cmca 7.679 (2) 17.127 (3) 17.210 (4) 2263.3 (8) 8 0.71069 (Mo Ka) 1.35 960 22-24 2.15 0.039 0.055
Table 11. Positional (X lo4) and Equivalent Isotropic Displacement Parameters (A2 X IO') for C6H4(NH),P(0)Ph (3A) atom X Y Z v P(1) 4586 (1) 2500 9233 (1) 39 (1) 2500 9951 (2) 47 (1) 0(1) 5342 (1) 4075 (3) 9772 (2) 45 (1) N(l) 4002 (1) 4675 (2) 2500 7202 (3) 48 (1) C(l) 6524 (4) 77 (22) 2500 C(2) 5373 (2) 107 (2) 2500 4928 (6) C(3) 5428 (3) 2500 4049 (5) 107 (2) C(4) 4794 (4) 2500 4706 (5) 101 (2) C(5) 4116 (3) 2500 C(6) 4043 (2) 6283 (4) 71 (1) 3416 (3) 10638 (2) 45 (1) C(7) 3398 (1) 4353 (4) 11413 (3) 60 (1) C(8) 2855 (1) 2305 (1) 3401 (4) 12203 (3) 72 (1) C(9)
'Equivalent isotropic U defined as one-third of the trace of the orthogonalized U, tensor. 1
2
3
preparation of 2 (R = MeC6H4) from t h e 1,2-(NH2)2C6H4/ MeC6H4P(OPh)2 reaction; however, the characterization was inconclusive. Even the oxide 3 has been only partially characterized.4v5 We now wish to report recent studies of these systems and t h e discovery that 3 can be obtained in two polymorphic crystalline forms. Experimental Section Apparatus and Materials. 31Pand 'H NMR spectra were recorded with a JEOL FX-90Q spectrometer at 36.5 and 90.0 MHz, respectively. 31P and 'H NMR chemical shifts downfield from 85% H'PO4 (external) and (CH3)4Si (internal) are reported as positive (+6). IR spectra (4000-400 cm-I) were obtained with a Beckman 4250 grating spectrometer. Mass spectra were obtained at 70 eV with a VG Analytical 7070 EQ-HF spectrometer. Elemental analyses were performed by Huffman Laboratories Inc., Wheatridge, CO. All manipulations were carried out by using standard glovebag techniques under dry N2.6 1,2-(NH2)2C6H4(Aldrich) was recrystallized from toluene. Et,N (Baker) was distilled from CaH2. Toluene (over Na/Pb alloy) and CH2C12(over P4010)were distilled before use. PhPCI2 (Strem Chemicals) was distilled from CaH2. PhP(O)CI2 (Aldrich) was used as obtained. PhP(OPh)2, prepared as described previously,' after vacuum distillation contained ca. 3% (m/m) PhP(O)(OPh), (by 'IP NMR). (a) Bent, E. G.; Barendt, J. M.; Haltiwanger, R. C.; Norman, A. D. Inorganic and Organometallic Polymers; ACS Symposium Series 360; American Chemical Society: Washington, DC, 1988; p 303. (b) Barendt, J. M.;Bent, E. G.; Haltiwanger, R. C.; Norman, A. D. J. Am. Chem. Soc., in press. Barendt, J. M.;Haltiwanger, R. C.; Norman, A. D.Inorg. Chem. 1986, 25, 4323. Pilgram, K.; Korte, F. Tetrahedron 1963, 19, 137. Dannley, R. L.; Wagner, P. L. J. Org. Chem. 1961, 26, 3995. Gutmann, V.;Hagen, D. E.; Utvary, K. Monatsh. Chem. 1%2,93,627. Shriver, D. F.; Drezdzon, M. A. The Manipulation of Air Sensitive Compounds, 2nd ed.; Wiley-Interscience: New York, 1986. Petrov, K. A.; Evdakov, V. P.; Bilevich, K.A.; Kosarev, Yu. S. Zh. Obshch. Khim. 1962, 32, 1974; Chem. Abstr. 1963, 58, 4596b.
Table 111. Positional ( X lo4) and Equivalent Isotropic Displacement Parameters (A2 X IO') for C6H4(NH),P(0)Ph (3B) atom X V z v 0 2078 (1) 2042 (1) 41 (7) 2338 (3) 0 2865 (3) 50 (2) 2428 (2) 1550 (5) 1472 (2) 46 (2) 1037 (5) 0 2000 (5) 45 (3) 0 620 (6) 2687 (6) 71 (4) -200 (7) 0 2648 (9) 97 (6) -578 (7) 0 1958 (9) 97 (5) -168 (7) 0 1280 (9) 90 (5) 641 ( 5 ) 0 1294 (5) 63 (4) 2943 (3) 908 (6) 913 (3) 40 (2) 399 (3) 53 (2) 1820 (8) 3408 (4) -97 (4) 63 (2) 894 (8) 3887 (4) 'See footnote a, Table 11. [C6H4N2(PPh)2]2was obtained as described elsewhere.' C6H4(NH),P(O)Ph (3). Polymorph 3A. 1,2-(NH2)2C6H4(17 "01) and PhP(OPh)2 (17 mmol) were heated in vacuo at 120 "C. After 18 h, "P NMR spectral resonances occur at 8 157.8 (PhP(OPh),), 110.5 (4), 26.5 (3), and 12.8 (PhP(O)(OPh),) (mol % 69:16:10:5). Upon further heating, the resonance at 6 110.5 (4) decreased in intensity. Cooling to 25 "C precipitates 3 from the reaction mixture as 3A (yield 1.4 g, 33% yield). Attempts to isolate 4 failed. PhP(O)CI2 and 1,2-(NH2)2C6H4were allowed to react in PhBr as described previ~usly.~ Recrystallization of the product from CHCI3 gave 3A (mp 278-279 OC; >85% yield, lit.4 yield 100%). "P{lH) NMR ((CD,),SO): 6 25.5 (s). 'H NMR: 8 9.09 (s). IR (KBr, cm-I): 3182 (s, N-H), 1260 (s, P=O).5 MS: m / e 320 (M+, C 1 2 H I I N 2 0 P )Anal. . Calcd for CI2HllNZOP:C, 62.60; H, 4.82; N, 12.17; P, 13.46. Found: C, 62.50; H, 4.94. 3 is only slightly soluble in toluene and CH2C12 and soluble in Me2S0. Polymorph 3B. Crystallization of [C6H4N2(PPh)2]2, prepared from the 1,2-(NH2),C6H4/PhPCI2 reaction in toluene,' from the toluene reaction solution yields trace quantities of 3 (
