3336 93, 5236 (1971). (8) R. Sarma, F. Ramirez, B. McKeever, J. F. Marecek, and S. Lee, J . Am. Chem. Soc., 98, 581 (1976). (9) R. D. Spratley, W. C. Hamilton. and J. Ladell, J . Am. Chem. Soc., 89, 2272 (1967). (10) W. C. Hamilton, J. S.Ricci, Jr., F. Ramirez, L. Kramer, and P. Stern, J. Am. Chem. Soc., 95, 6335 (1973). (11) D. Hellwinkel, W. Krapp, D. Schomberg, and W. S. Sheldrick, Z. Naturforsch., in press. (12) (a) W. S. Sheldrick, A. Schmidpeter, and J. H. Weinmaier. Angew. Chem., 87, 519 (1975); (b) personal communication. (13) M. Eisenhut, R. Schmutzler, and W. S. Sheldrick, J . Chem. Soc., Chem.
(14) (15) (16) (17)
Commun., 144 (1973), and personal communication. R. R. Holmes and J. A. Deiters J . Am. Chem. SOC.,99, 3318 (1977). R. S. Berry, J. Chem. Phys., 32, 933 (1960). R. R. Holmes, Acc. Chem. Res.. 5, 296 (1972). E. L. Muetterties. W. Mahler, and R . Schmutzler, Inorg. Chem., 2, 613
(1963). (18) (a)R. R . Holmes, J. Am. Chem. Soc., 96, 4143 (1974); (b) ibid., 97, 5379 (1975). (19) J. A. Howard, D. R . Russell, and S.Trippett, J. Chem. SOC.,Chem. Commum, 856 (1973). (20) (a) M. Wieber and W. R. Hoos, TetrahedronLett.,4693 (1969);(b) Monatsh. Chem., 101, 776 (1970).
Crystal and Molecular Structure of Oxyphosphoranes. 9. The Spiropentaoxyphosphorane, ( P o5 )(CF 3C=CCF3 )(C6H4)(c6H 5 Poojappan Narayanan,2a Helen M. Berman,2a Fausto Ramirez,*2b James F. Marecek,2b YuFen Chaw,2b and Vidyanatha A. V. Prasad2b Contributionfrom The Institute f o r Cancer Research, Philadelphia, Pennsylvania 191 I I , and the Department of Chemistrj,, State Uniuersity of New York at Stony Brook, Stony Brook, New York I 1794. Receired July 28, 1976
Abstract: 2-Phenoxy-2,2-o-phenylenedioxy-4,5-b~s(trifluoromethyl)-2,2-dihydro-1,3,2-dioxaphospholene (12) crystallizes from hexane in the triclinic system, space group P1. There are two molecules, C16H905PF6, in the unit cell (Z = 2) of dimensions a = 6.105(3), b = 12.130-(8), c = 12.037 ( I O ) A, 01 = 85.35 ( 6 ) , /3 = 101.00 ( 6 ) ,y = 98.54 ( 6 ) ’ . Intensities for 3130 reflections here measured on a f 1 diffractometer (Cu Kn) by 8/28 scan techniques. The structure was solved by direct methods ( M U L T A ~program), and refined to a final R of 14.7%for 1706 reflections by full-matrix least-squares methods. Bond angles around the phosphorus atom in 12 deviate significantly from those of the ideal trigonal bipyramid (TBP), tetragonal pyramid (TP), and 30°-turnstile rotation configuration (3O0-TR). Bonds connecting the phosphorus to constitutionally identical ligands in 12 cannot be classified as apical and equatorial in terms of their lengths within the accuracy of the measurements. T o characterize the skeletal geometry of 12, and of other phosphoranes with similar properties (“non-TBP phosphoranes”), the term “xO-TR configuration” is proposed. The x’-TR represents the accommodation of all bond angles and distances in the molecule to the electronic and steric demands of the ligands. The direction, but not the magnitude, of the deviations from the ideal TBP found in the actual xO-TR can be rationalized in terms of the T R mechanism for permutational isomerization of phosphoranes.
Spirophosphoranes, 1-6, with five oxygen^,^-^ four oxygens and one n i t r ~ g e n , three ~ - ~ oxygens and two nitrogen^,^,^ and two oxygens and three nitrogen^^%^-^ as ligands to the phosphorus have been prepared from the reaction of fivemembered cyclic phosphites or phosphoroamidites with adiketones, o-quinones, monoketones, or monoaldehydes. The geometry around the phosphorus in these compounds has not been established by physical method^.^
A second type of spirophosphorane is based on two catechol bidentate ligands”J*l’plus one additional oxygen,” 7 , fluorine,’* 8, or carbon,13 9, ligand.
x 7, X = OC,H->
8.X=F 9. X = CH
1, X = OC,H, OCH,
2,X
=
3, X = OCH,
3
N(CHJI, X
3
4, X = N(CH,),, S
5, X = OCH, 6, X
=
3
N(CH,)?, N
Journal of the American Chemical Society
/
99:IO
/
Considerable interest has been aroused by the finding that the geometry around phosphorus in compounds of this type, 8,14 9,15 and 7 , l b does not resemble that of the regular TBP,16 which has been observed in other types of acyclic and monocyclic oxyphosphoranes,I7 by x-ray crystallography. The skeletal geometries of spirophosphoranes 8 and 9 have been described in terms of the regular TPI6 (or square pyramid), or of “mixes” of TP and TBP.’4,15,’8,19 The results of x-ray analysis of other spirophosphoranes with two five-membered rings and combinations of oxygen, sulfur, and carbon ligands,20.21and with a four- and a five-membered ring and oxygen and carbon ligands,2* have also been interpreted in this m a n r ~ e r . ~More ~ , * ~recently the term static x o - T R configurationL6was applied to a description of the geometry of spirophosphorane 7.1b317.25 M a y 1 I , 1977
3337 Table 1. Atomic Coordinates ( X IO4 for Nonhydrogen. X IO3 for Hydrogen Atoms) and Thermal Parameters ( X I O 3 for Anisotropic Atoms) for Compound 12a
3887(3) 4018 (7) 1235 ( 7 ) 5441 (8) 5416 (8) 3410(7) 2135 ( I I ) 521 ( 1 1 ) 6334 ( I 2) 5908 (12) 4763(12) - 1523 I I ) - I874 13) -255 14) I800 12) 8528 1 3 j 9458 17) 8244 18) 6000 20) 5050 15) 472 I 15) 7678 16) 3008 14) 4599(18) 6394(17) 9599 ( I O ) 7110(14) 8101 (13) X -275 -33 I -52 305 945 1108 893 500 34 1
7148(1) 6293 (4) 7248 (4) 8169 (4) 6319 (4) 7749(4) 6217 (6) 6788 ( 7 ) 9 I66 (6) 6670 ( 7 ) 7464(6) 6845 (8) 6303 ( 8 ) 5749 ( 8 ) 5675 ( 7 ) 9254i8j IO286 (9) 11103 (8) I1007 (8) 9996 (8) 8156(10) 6099 ( 9 ) 8582(8) 7501 (8) 8799(7) 6249 (7) 4985(7) 6391 (9)
6542(1) 5578 (4) 6036 ( 4 ) 6056 ( 4 ) 7420 (4) 7678(4) 4712 (6) 4999(6) 658 1 (6) 8502 ( 6 ) 8667(6) 4292 (7) 3265 ( 7 ) 3028(7) 3741 (6) 7 1 3 3 (81 7620 (9) 7583 ( I O ) 7003 (9) 6521 (8) 9622 ( 7 ) 9251 (8) 9537 ( 7 ) 10552(5) 9903(lO) 8873 (6) 9272(7) 10280(5)
Y
2
728 633 537 526 867 1031 1 I79 I I64 993
445 274 227 362 712 802 803 682 61 I
4.1 I ( 6 ) 3.53 (16) 3.12 (15) 5.12 (19) 5.42 ( I 9) 4.72 ( 1 7) 4.60 (26) 4.16 (24) 5.59 (29) 5.37 (30) 5.53 (29) 3.14 (25) 4.68 (31) 5.77 (35) 5.21 (30) 4.28 (3oj 5.59 (42) 8.79 (51) 12.09 (60) 6.49 (38) 5.41 (37) 7.59 (41) 15.53 (42) 29.00 (75) 15.31 (56) 5.62 (23) 10.74 (41) 13.88 (40) B 5.0 6.0 5.0 5.0 5.0 9.0 7.0 7.0 6.0
4.99 (8) 6.45 (24) 7.13 (22) 4.60 (23) 6.05 (24) 6.22 (24) 5.43 (30) 5.41 (39) 4.46 (35) 6.93 (36) 5.58 (37) 8.70 (48) 8.41 (52) 7.06 (45) 5.12 (41) 6.02 (48) 10.40 (54) 7.79 (46) 5.14 (40) 7.44 (42) 14.39 (71) 7.81 (55) 2 I .99 (46) 12.16 (51) 20.60 (50) 14.64 (48) 10.25 (40) 18.86 (68)
4.28 (6) 4.70 ( I 9) 4.75 (20) 5.20 (20) 3.55 ( I 8) 3.45 ( I 8 ) 4.04 (28) 3.72 (26) 4.26 (28) 3.65 (31) 3.70 (30) 5.75 (35) 4.25 (31) 4.05 (33) 4.64 (29) 8.78 (50) 10.26 (56) 7.62 (54) 7.79 (54) 7.19 (43) 4.37 (33) 5.41 (38) 10.08 (33) 5.18 (27) 18.23 (49) 10.57 (37) 14.16 (53) 5.17 (27)
Numbers in parentheses are estimated standard deviations in the least significant digits. exp[-I/4(Bllh2a*’ B22k2h*? B ~ ~ I ? c *2B12hka*b* ~ 2B13h/a*c* 2B&/b*c*)].
+
A?
+
+
+
This paper reports the x-ray crystallographic analysis of a spirophosphorane, 12, which combines the structural features of the two types of compounds, 1 and 7, previously synthesized. The incorporation of one catechol bidentate ligand into the 1,3,2-dioxaphospholene ring is achieved by reaction of hexafluorobiacetyl (10) with phenyl o-phenylene phpsphite.26
10
11
12
Experimental Section Preparation of 2-Phenoxy-2,2-o-phenylenedioxy-4,5-bis(trifluoromethyl)-2,2-dihydro-1,3,2-dioxaphospholene(12). The compound was prepared as described.26 The crystals for x-ray analysis were obtained by dissolving 600 mg of the substance in 6 mL of hot hexane and allowing the solution to cool to 21 OC undisturbed: mp 85-86 O C ; 631R +29.5 ppm vs. H3P04 0; 619F-12.9 ppm vs. CF3COOH 0 (both a t 25 OC in CHzCll solution). Crystal Data. Compound 12: C I ~ H ~ O ~triclinic; P F ~ ;P r ; a = 6.105 ( 3 ) , b = 12.130(8),c = 12.037 ( I O ) & a = 85.35 ( 6 ) , p = lOl.O0(6), y = 98.54 (6)’; Z = 2.
Berman, Ramirez, et al.
+
1.12 (5) 1.17 (17) 1.43 (15) 0.12 (17) 1.75 (18) 1.52 (18) 0.79 (23) 0.44 (25) 1.05 (26) 0.86 (27) 0.88 (28) 0.92 (29) 0.90 (33) -0.38 (32) 0.87 (29) 0.78 (31) -0.43 (39) -0.77 (41) 2.76 (45) 2.55 (36) 1.74 (43) 2.55 (43) 10.58 (58) 8.06 (58) -7.52 (45) 3.43 (30) 2.97 (35) 8.50 (55)
0.88 (5) 0.16 (15) 0.56 ( 16) 1.57 (17) 0.15 (15) 0.86 ( 1 6 ) 0.50 (24) I .05 (22) 1.12 (24) 0.19 (25) 0.99 (27) 0.50 (25) -0.25 (26) 0.31 (29) I .02 (25) 0.83 ( 3 4 ) 1.50 (42) 2.60 ( 4 8 ) 3.32 (54) 0.91 (35) -0.47 (29) 0.21 (34) -0.98 (37) 4.76 (43) 7.64 (581 0.28 (24) -0.37 (36) -2.05 (26)
-0.85 (5) -2.06 ( I 9) - 1.80 (19) -1.30(18) -0.24 ( 1 7) -0.95 ( 1 8) -0.75 (24) -0. I8 (27) -0. I7 (26) - I .05 (27) - 1.25 ( 2 8 ) -0.21 (33) -0 36 (34) - 1.93 (32) - I .24 ( 2 8 ) -1.83 (41) -4.56 (51) -2.05 (42) 0. I 2 (39) -0.32 (36) -2 87 (41) 0.05 (40) -8.82 (50) 0.03 (3 I ) -15.04 (78) -1.35 (36) 4.05 (40) -1.61 (37)
Anisotropic thermal parameters are of the form Isotropic hydrogen thermal parameters are in
Data Collection and Structure Determination. The crystals were extremely sensitive to atmospheric moisture and decomposed within a few minutes when exposed to air. Crystals were handled under a constant flow of argon and sealed in glass capillaries. Intensity data were collected on a PI diffractometer using Cu Ka radiation by 8/20 scan technique. Four different crystals were necessary to collect the data, since the crystals deteriorated rapidly. The data sets were averaged, and of 3130 unique reflections 1706 had (F,12 > 2a(lF,12). Neither absorption nor extinction corrections were applied. The structure was solved by direct methods using the program MULTAN2’ and refined by full-matrix least squares to an R value of 14.7%. The positions of hydrogen atoms were calculated but not refined. The final positional and thermal parameters are given in Table I . The observed and calculated structure factors are available as supplementary material.
Results The atoms in compound 12 are numbered as shown in Figure 1 , which includes the bond distances and angles. Some intramolecular nonbonded distances are given in Table 11. Equations of least-squares planes, the deviations of certain atoms from the planes, and the dihedral angles between planes are collected in Tables 111 and IV. An isolated molecule is shown in Figure 2. The data disclose that the geometry around the phosphorus in 12 does not resemble that of an ideal TBP with D3h sym-
/ Crystal and Molecular Structure of (P05)(CF3C=CCF3)(C6H4)(CsH5)
3338
fi4 1267
P
04
01
P
05
165.9
02
P
03
110.0
02
P
04
139.0
1.356
1.377
2
:,393
I
59-1
128 2
05 C 3
I377
05 (15 P F152
F151 (15
F153
109.3 98 6 112 6
C16F162
1111
F161 C i 6 F163
107.7
C4 2 112.2
P3
84.8'
01
1130 01
Yo
.s 2
\
Q
3
1
III
%
Figure 3. I , ideal TBP. I I , ideal TP. I l l . general representation of irregular ("non-TBP") phosphoranes; P and ligand pair (4,s) are on the plane of the paper and ligands of trio (3.1,2) are on successive planes parallel to
it. R1 1 2 5 l6
F 151
, 326
102.7
I200
F 153
I320 F
IO3
107.6
Table 111. Least-Squares Planes in Compound 12
F
1.344
+ +
61
Figure 1. Numbering system. and bond distances and angle5 in spirooxyphoaphoranc 12. The esd's for phosphorus bond distances are 0.005 A, and for bond angles 0.3': for C - 0 bond distances 0.009 A,bond angles 0.4': for bcnrcne ring, bond distances 0.010 A. bond angles 0.7'; for trifluoromcthql groups. bond distances 0.012 A,bond angles 0.9".
Figure 2. Computer-generated drawing of the molecule of the spirooxyphosphorane 12. Wote deviations from ideal skeletal TP geometry disclosed by t h e tuisted spirobicyclo system.
Table 11. Selected Intramolecular Nonbonded Distances 8, in Compound 12 O( I )
* * O(4) O(2) . . .O ( 5 ) O(4) * * * 0 ( 5 ) C(IO)..*O(3) 0(1)...0(2) C(14)..*0(3) O(1) * * O(3) O(3) * O ( 5 ) P * * * C(2)
2.220 2.234 2.338 2.360 2.362 2.386 2.387 2.487 2.504
P * * * C(4) P . . C(1) P * * C(5) O(2) * * * 0 ( 3 ) O(3) * * * O(4) P * * C(3) C(3) * * * 0 ( 5 ) C(14) .. . O ( 5 ) O(2) . * * 0 ( 4 )
.
2.51 I 2.533 2.560 2.640 2.67 1 2.670 2.740 3.078 3.080
metry. Figure 3-1 shows the placement of the oxygen ligands of 12 on a hypothetical T B P skeleton, with O(4) and O(5) of the phospholene ring, and O( 1 ) and O(2) of the benzophospholene ring, occupying apical-equatorial positions for reasons Journal of the American Chemical Society
/ 99:lO / M a y
A. Coefficients, A , B, c', D,of the Equation of Plane, Ax By c'z -tD = 0, and Deviation in A of Individual Atoms from Planes; x, y, and 2 Are Relative to the Orthogonal Axes. Plane 1 : P-O(2)-O(3)-0(4) -0.275; 0.579: 0.768; - I 1.254 O(2) = 0.003; O ( 3 ) = 0.002; O ( 4 ) = 0.003; P = -0.008 Plane 2: P - 0 ( 1 ) - 0 ( 2 ) - 0 ( 5 ) 0.320: 0.819: -0.477; -3.417 O( I ) = -0.069; O ( 2 ) = 0.003; O ( 5 ) = -0.067: P = 0.1 34 Plane 3: P-O( 1 ) - 0 ( 3 ) - 0 ( 5 ) 0.775; -0.285; 0.565; -1.490 o(I)= 0.006; O(3) = 0.002; O ( 5 ) = 0.006; P = -0.014 Plane 4: P - 0 ( 1 ) - 0 ( 4 ) - 0 ( 5 ) 0.744; 0.650; -0.157; -4.195 O( I ) = -0.066: O(4) = 0.006; O ( 5 ) = -0.064; P = 0.123 Plane 5: O( 1)-O(2)-O(4)-O(5) 0.55 I ; 0.765; -0.333: -3.697 O(1) = 0.186; O ( 2 ) = -0.184; O ( 4 ) = -0.188; O(5) = 0.186; P = 0.389 Plane 6: P-O(4)-0(5)-C(4)-C(5) 0.722; 0.675: -0.155; -4.49 I O(4) = -0.080; O ( 5 ) = -0.07 I ; C(4) = 0.044; C(5) = 0.029: P = 0.078 Plane 7: P-O(1)-0(2)-C(l)-C(2) 0.333; 0.794; -0.509: D = -2.999 O( I ) = -0.064: O ( 2 ) = -0.064; C ( 1 ) = 0.029; C(2) = 0.030; P = 0.069
B.' Deviations from the Planes of the Phosphorus Atom That Is Not Included in the Plane Calculation Plane 12 O( I )-O(2)-0(3) P = 0.762 Plane 13 O( I )-O(2)-0(4) P = 0.554 Plane 14 O( 1)-O(3)-0(4) P = -0.797 O( I )-O(2)-0(5) Plane 15 P = 0.203 Plane 16 O( I)-O(4)-0(5) P = 0.191 Plane 17 O(2)-O(3)-O(5) P = -0.793 Plane 18 O(2)-O(4)-0(5) P = 0.568 Plane 19 O(3 ) - 0 ( 4 ) - 0 ( 5 ) P = -0.764 0 Planes numbered 8-1 I are three-atom planes defined i n Table IV for calculation of dihedral angles.
previously discussed.3-*5 The differences between ideal and observed bond angles in 12 are summarized in Table V. The corresponding values for the three related spirophosphoranes 7-9 and for the nearly regular TBP 13'' and 1428are included in Table V. Other noteworthy features of the molecular structure of 12 are: ( I ) The endocyclic P-0-C angles have comparable values 11, 1977
3339 Table IV. Some Dihedral Angleso in Compound 12 Plane a
Atoms
Plane b
Atoms
6
P-O(4)-0(5)-C(4)-C(5)
9
P-O( 1 )-0(4)
7
P-O( 1)-0(2)-C( 1 )-C(2)
IO
P-O(2)-0(5)
1
P-O(2)-O(3)-0(4)
2
P-O( I )-O(2)-0(5)
1
P-O(2)-O(3)-0(4)
3
P-O( 1)-O(3)-O(5)
1
P-O(2)-O(3)-0(4)
4
P-O( I)-O(4)-0(5)
2
P-O( 1 ) - O ( 2 ) - 0 ( 5 )
3
P-O( 1 ) - O ( 3 ) - 0 ( 5 )
2
P-O( I )-O(2)-O(5)
4
P-O( 1)-O(4)-0(5)
3
P-O( 1 ) - O ( 3 ) - 0 ( 5 )
4
P-O( 1 )-O(4)-0(5)
3
P-O( 1)-O(3)-0(5)
5
O( I)-O(2)-O(4)-0(5)
5
O( 1 )-O(2)-O(4)-0(5)
12
O( I ) - O ( 2 ) - 0 ( 3 )
5
O( I ) - O ( 2 ) - 0 ( 4 ) - 0 ( 5 )
14
O( 1 ) - O ( 3 ) - 0 ( 4 )
5
O( I )-O(2)-O(4)-O(5)
17
O(2)-O(3)-0(5)
5
O(I ) - 0 ( 2 ) - 0 ( 4 ) - 0 ( 5 )
19
O(3)-O(4)-0(5)
6
P-O(4)-0(5)-C(4)-C( 5 )
7
Angle, deg
P-O( I)-O(Z)-C( I)-C(2)
" Angles between the normals of the planes which are defined in Table IV. rodicatecholphenoxyphosphorane ( 7 ) , ref 1 b.
Values in parentheses refer to the corresponding angle in spi-
Table V. Deviations from Ideal Trigonal Bipyramid (TBP) in Spirooxyphosphoranes and in Acyclic (13) and Monocyclic (14) Oxyphosphora nes Compd Angle. deg
Deviation from, deg
0(2)-P-X(3)a O( l)-P-O(5) 0(4)-P-0(5) O( I ) - P - 0 ( 4 ) X(3)-P-0(4) 0(2)-P-0(4) O( l)-P-X(3) X(3)-P-0(5) 0(2)-P-0(5) O( I)-P-O(2)
120 I 80 90 90 120 120 90 90 90 90
120
S6
7c
13"
9d
14, ~~
-IO -14 -1
-5 -9 +19 +5 +9
-6 +2
-13 -12 $2 -4 -13 +26 +6 $6 -5 +I
-17 -20 +2 -7 -15 $3 1 $12 +8 -7
-14 -23 +I -7 -14 $28 $12 +I I -7 0
+1
-4 -3
-3 -2 -I
-1
-2 $5 -2 $2 -2
-1
-3 +5 +I -2 +I $3
$1
$2
(' Present work. Spirodicatecholfluorophosphorane; ref 12 and 14. Spriodicatecholphenoxjphosphorane; ref 1 b. Spirodicatecholnirrhjlphosphorane. One of two independent molaxles in the asymmetric unit; the other shows similar deviations ( < 1.5' in all angles); ref 1,3.2-dioxaphospholene: ref 28. I3 and 15.
