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An answer to the spiro versus ansa dilemma in cyclophosphazenes
Journal of Molecular
220 (1990) 63-77 B.V., Amsterdam - Printed
63
Structure,
Elsevier Science Publishers
in The Netherlands
AN ANSWER TO THE SPIRO VERSUS ANSA DILEMMA IN CYCLOPHOSPHAZENES Part XIII*. Synthesis and crystal structure of the first diMACROSPIRO and di-MEGASPIRO species from di- and trioxodiamines FRANCOIS SOURNIES, LABARRE** CNRS, Laboratoire Toulouse (France)
ABDELAZIZ
Structure
EL BAKILI, BRUNO ZANIN and JEAN-FRANCOIS
et Vie, FacultP de Pharmacie,
35, rue des Maraichers,
31400
JOEL JAUD Laboratoire
de Chimie de Coordination,
205, route de Narbonne,
31400 Toulouse (France)
(Received 30 May 1989)
ABSTRACT Aminolysis of N,P,Cl, by dioxodiamines and trioxodiamines in suitable conditions yields diMACROSPIRO and di-MEGASPIRO species which constitute new di-macrocyclic monocyclophosphazenic architectures. X-Ray structures of di-SPIRO derivatives from 4,9-dioxadodecane1,12-diamine and from 4,7,10-trioxatridecane-1,13-diamine reveal two highly unsymmetrical 15 and 16.membered loops, respectively, grafted on the same N,P, ring.
INTRODUCTION
Reactions of N3P3C16with oxodiamines such as the 3-oxapentane-l,&diamine (coded as 202)) the 3,6-dioxaoctane-l&diamine (20202), the 4,7-dioxadecane-l,lO-diamine (30203)) the 4,9-dioxadodecane-1,12diamine (30403 ) and the 4,7,10-trioxatridecane-1,13-diamine (3020203) have been investigated in the very recent past in our laboratory with the aim of designing cyclophosphazenic two-ring bridged assembly structures (coded as Barrelanes and cousins [ 1]) which would display a high solubility in common organic solvents and then which could be used for the synthesis of one-dimensional materials for further applications. Actually, these oxodiamines lead surprisingly to monocyclophosphazenic species in which the oxodiamino ligand is grafted either as a SPIRO loop onto one P atom of the N3P3 ring or as an ANSA arch onto two P atoms of the ring. Syntheses are highly stereoselective and even stereospecific in some cases and *For Part XII see ref. 8. **Author to whom correspondence
OOZZ-2860/90/$03.50
should be addressed.
0 1990 Elsevier Science Publishers
B.V.
64
whether the SPIRO or ANSA configuration is obtained depends very much on the solvent used. For example, reaction of 202 with N3PJ& in acetonitrile quantitatively yields the ANSA 202 derivative [2-41, reaction of 20202, 30203 and 30403 in THF lead to the MACRO-SPIRO moieties [ 5-71 while MACRO-ANSA isomers are obtained by using a toluene/Na,CO, interface process [ 5-71. Similarly, reaction of 3020203 with N3P3C& either gives the MEGA-SPIRO species [8-lo] or its MEGA-ANSA isomer [8] depending on experimental conditions. It must be pointed out that the whole structures we just mentioned are either MONO-SPIRO or MONO-ANSA compounds, that is molecules in which one SPIRO loop or one ANSA arch is grafted onto the N3P3 ring. Moreover, these amazing macrocyclic architectures are very major products in every case, the expected two-ring bridged assembly structures just being observed from time to time as very minor side-products. In other words, the synthesis of barrelane-like dicyclophosphazenic species constitutes a challenge waiting to be taken up. The present paper reports on the synthesis and crystal structure of some DISPIRO derivatives from oxodiamines which were obtained by a concerted use of experimental conditions described above for synthesizing the MONO-SPIRO compounds from oxodiamines and of synthetic procedures which had been found to be very successful for obtaining POLY-SPIRO entities from nonoxygenated diamines (according to BASIC rules) [ 111. EXPERIMENTAL
Preliminary remarks The synthesis of MONO-SPIRO compounds proceeds cleanly, as mentioned above, upon reaction of oxodiamines on N3P3C16in (1: 1) stoichiometric conditions and by using a toluene/Na$O, interface process. It could be expected that the corresponding DI-SPIRO moieties would be obtained in the same way when working in (2 : 1) conditions. Actually, this is not the case at all; a 100% excess of oxodiamine with respect to the stoichiometry for the synthesis of MONO-SPIRO derivatives, (i) yields stereospecifically the MONO-SPIRO entity in the case of 30203 (Table 1) and (ii) reveals new complex molecular structures as major derivatives (in addition to the expected MONO-SPIRO one as a minor by-product) in the case of 30403 [ 12,131. It was therefore decided to re-investigate the nature of solvent(s) which would lead to the production of DI-SPIRO species. Despite the severe discrepancies noticed regarding the chemical behaviour of dioxodiamines and of nonoxygenated diamines versus N3P3C16,the production was attempted of DISPIRO derivatives from the former by using the petroleum-ether/dichloromethane (7 : 3) mixture (solvent S) which had been so efficient for the synthesis of the DI-SPIRO cousins from the latter [ 141. Under such conditions, the DI-SPIRO compounds can be obtained from ox-
65
TABLE 1 Synthetic pathways for producing di-MACROSPIRO and di-MEGASPIRO compounds
TOLUENE-WATER _____F
N3P3C’6
mono-MACROSPIRO
30203
TO~~~~~,--~~:~OS~R~~~203 (whatever
stoichiometry
CASE
(yield 100%)
(yield
loos/.)
is)
OF THE
OXODIAMINE
30203
TOLUENE-WATER N3P3Clg
-w
mono-MACROSPIRO
S:L;E;x
SOLVENTS
(yield 50%)
CASE
OF THE
x
1
(yield 40%)
2:1
di-MACROSIPIRO
OXODIAMINE
30403
30403
(yield 60%)
30403
TOLUENE-WATER N3P3C’6
__
CASE
mono-MEGASPIRO
OF THE
OXODIAMINE
3020203
(yield 90%)
3020203
odiamines (i) either from their MONO-SPIRO parents by working in solvent S (Table l), or (ii) from N3P3C16itself (only for 30403, Table 1) but with a rather poor yield in this case. Table 1 gathers the different pathways which can be used to obtain DI-SPIRO compounds from oxodiamines and it may be noticed that chemical processes run “accordingly or not” to the rules of the BASIC chemical game (the solvent S is a common solvent for the synthesis of BASIC systems when the toluene/ water interface process is not ) .
66
Synthesis of di-MACROSPIRO (30403) The synthesis of the title compound may run in solvent S according to the pathway (Table 1) lN,P,C& + 5 (30403) =>di-MACROSPIRO
(30403)
+ (30403.2 HCl)
A large excess of the dioxodiamine is then needed for making the reaction complete. 14.74 g of (30403) in solution in 500 ml of solvent S were added in a single operation to a solution of 5 g N,P,Cl, in 1000 ml S. The trioxodiamine dihydrochloride precipitates immediately and in time forms a waxy deposit on the walls of the vessel. The reaction takes 24 h and was considered complete when the 31PNMR singlet of N3P3C16at 20.09 ppm had disappeared. The clear organic phase was then poured off and the solvent was removed in vacua at 25’ C to give a light yellow syrup (60% yield) containing about 90% of the diMACROSPIRO (30403) derivative and 10% of its mono-MACROSPIRO parent. The major expected di-MACROSPIRO compound was separated from the minor mono-MACROSPIRO moiety through a single SiO, column chromatography using acetonitrile as the eluant (Rf=0.60 and 0.90, respectively, for the di-MACROSPIRO and mono-MACROSPIRO derivatives). Pure diMACROSPIRO (30403) appears as a viscous liquid owing to its clathration with solvents which were used. Stirring for one night with n-heptane gave a white powder which crystallized in Ccl, (final yield 50%) F = 107 oC ) . The 31PNMR spectrum, as recorded on Bruker AC 200 equipment, in CDC13 reveals the P (MACROSPIRO) doublet centred on 13.37 ppm and the P (Cl,) triplet centred on 24.58 ppm, “Jpp = 48.7 Hz. The DC1 mass spectrum was recorded on a NERMAG RlOlO-H quadrupole mass spectrometer. The molecular ion MH+ is correctly observed at m/z 610 with a satellite distribution confirming the presence of two chlorine atoms in the molecule. Synthesis of di-MEGASPIRO (3020203) In toluene/water interface the synthesis of the title derivative may run according to the pathway (Table 1) 1 N3 P3Cls + 5.25 (3020203) *di-MEGASPIRO
(3020203)
+ (3020203.2
HCl)
A large excess of the trioxodiamine is then needed for making the reaction complete. 33.26 g (3020203) dissolved in 500 ml solvent S were added in one operation to a solution of 10 g N,P,Cl, in 1000 ml S. The trioxodiamine dihydrochloride precipitates immediately and in time forms a waxy deposit on the walls of the vessel. The reaction takes 24 h and was considered complete when
67
the 31P NMR singlet of N3P3C16at 20.09 ppm had disappeared. The clear organic phase was then poured off and the solvent was removed in vacua at 25” C to give a light yellow syrup (51% yield) containing about 80% of the di-MEGASPIRO (3020203) derivative and 20% of its mono-MEGASPIRO parent. The major expected di-MEGASPIRO compound was separated from the minor mono-MEGASPIRO moiety through a single SiOZ column chromatography using a (7 : 3 ) mixture of dichloromethane and 2-propanol as the eluant t&=0.56 and 0.27 for the DISPIRO and MONOSPIRO derivatives, respectively ). Pure di-MEGASPIRO (3020203 ) appears as a viscous liquid owing to its clathration with solvents which were used. Stirring for one night with nheptane gave a white powder which crystallized in Ccl, (final yield 20%, F=95”C). The 31PNMR spectrum, as recorded on Bruker AC 200 equipment, in CDC& reveals the P (MEGASPIRO ) doublet centred on 13.26 ppm and the P (CL) triplet centred on 24.06 ppm, ‘Jpp = 48.7 Hz. The EI mass spectrum was recorded on a NERMAG RlOlO-H quadrupole mass spectrometer. The molecular ion M+ is correctly observed at m/z 642 with a satellite distribution confirming the presence of two chlorine atoms in the molecule. The fragmentation pattern displays the classical “festooned” aspect which characterizes the mass spectrum of any SPIRO cyclophosphazene. Such a festooned look is due to successive losses of NH (m/z 15)) CH, (m/z 14) and 0 (m/z 16), links which prove that the two SPIRO loops are actually losing these links “pearl per pearl” upon electron impact. X-RAY STUDY
General remark-s In both cases studied below, a transparent colourless block has been chosen for data collection using an Enraf-Nonius CAD4 diffractometer. The angular coordinates of 25 hkl reflections were centred and least-squares refined to give the lattice parameters (Table 2). Details of data collection for the two compounds are reported in Table 2. Lorentz and polarization corrections were applied. In view of the low values of absorption coefficients, no absorption corrections were then performed. The structure of di-MACROSPIRO (30403 ) (coded as DS 30403 ) (Figs. 1, 2) was measured at room temperature (293 K) and a noticeable wobbling of several atoms in the molecule was observed, thermal parameters of some of the carbon and oxygen atoms at the “outer” ends of the macrocyclic loops being very large. Then, the structure of di-MEGASPIRO (3020203 ) (coded as DS 3020203) was recorded at 123 K with the aim of freezing any eventual wobbling. Actually, this attempt at the production of a well-localized structure at low temperature was not successful. Indeed, a substantial agitation remains at
68 TABLE 2 Physical properties and parameters for data collection and refinement DS 30403 Formula Mol. wt. Cryst. system Sptce group a (A) 5 (A) c (A) (Y (deg) P (deg) Y (deg) v (Aa) z dcalc(g cm-3) d,, (g cmm3) F(OOO) p (MO&X) (cm-‘) Temperature ( ’ C ) 1 (A) Take-off (deg) Detector width (mm) Scan type Scan width (deg) 0 range (deg) No. of measured reflections No. of variables, NV No. of unique refl., NO Agreement R R,
DS 3020203
W’,Q&W-L,
610.4 Triclinic
640.3 Triclinic
Pi
Pi
10.20(9) 12.51(8) 13.48(7) 71.9(2) 78.1(2) 69.0(l) 1518 2 1.330 1.33 648 4.0 20 0.71069 4.0 4x4
8.90(4)
13.55(5) 14.88(8) 111.4(3) 99.9(2) 108.3(4) 1501 n
‘
1.417 1.42 676 4.2 - 150 0.71069 3.2 4x4
ei2e
e/ze
0.8+0.35tan 0 o-22 1958 325 1677
0.85 + 0.35 tan 0 O-25 4968 352 3805
0.087 0.092
0.077 0.088
factors
the level of four atoms (namely Oi, C4, C5 and 02, Fig. 3) at the “outer” end of one of the two loops (notice that the equivalent atoms at the “outer” end of the other loop were perfectly fixed). Attempt at refinement of the structure in the non-centrosymmetric space group Pl were unsuccessful owing to emergence of huge correlations. Thus, it was arbitrarily decided to achieve the refinement in the centro-symmetric space group Pi which revealed the disorder on C, (i.e. two equivalent positions C& and C5n) but not the disorder on O,, C, and 0,. Despite this unsatisfactory conclusion, it was decided to report the structure of di-MEGASPIRO (3020203 ) as it is because it definitely supports the di-MEGASPIRO architecture which had been predicted by NMR and mass spectrometry.
69
C25
Fig. 1. Perspective view of di-MACROSPIRO (30403) quasi-perpendicular to the plane of the figure).
with numbering of atoms (N3P, ring
Fig. 2. Perspective view of di-MACROSPIRO (30403 ) with N,P, ring into the plane of the figure.
The structures were determined using direct methods leading to the localization of chlorine, phosphorus and nitrogen atoms. The carbon, oxygen and hydrogen atoms were located from different Fourier maps. Hydrogen atoms were added to the structure factor calculations as fixed at 0.97 A from their relative attached atoms with a value of 5.5 A” for isotropic temperature factors. Scattering factors were taken from Cromer and Waber [ 151 and anomalous
Cl8
Fig. 3. Perspective quasi-perpendicular
view of di-MEGASPIRO (3020203) to the plane of the figure).
with numbering
of atoms
(N,P,
ring
TABLE 3 Final positions and equivalent isotropic thermal parameters of di-MACROSPIRO Atom
r
Y
.z
S(A2)
Atom
x
Cl1 Cl2 Pl P2 P3 01 02 03 04 Nl N2 N3 N4 N5 N6 N7 Cl c2
0.8186(5) 0.5391(5) 0.6033(4) 0.6817(5) 0.7540(5) 0.224(l) 0.707(l) 1.033(l) 0.663(l) 0.670(l) 0.618(l) 0.757(l) 0.437(l) 0.680(l) 0.921(l) 0.689(l) 0.322(2) 0.180(Z)
0.1508(3) 0.3409(4) 0.3426(3) 0.3016(3) 0.4797(3) 0.2062(7) 0.0337(l) 0.6397(g) 0.8383(g) 0.4484(7) 0.2670(7) 0.3997(S) 0.3821(7) 0.2612(7) 0.467(l) 0.6239(g) 0.408(l) 0.417(l)
0.1952(3) 0.1319(3) 0.4286(3) 0.2314(3) 0.2673(3) 0.5311(6) 0.6828(s) 0.1261(g) 0.0504(g) 0.3794(7) 0.3461(7) 0.1918(7) 0.4741(7) 0.5352(7) 0.271(l) 0.2158(g) 0.411(l) 0.477(l)
6.9(l) 7.7(2) 3.6(l) 4.3(l) 4.7(l) 5.3(3) 4.8(3) 10.0(5) 9.7(5) 4.0(3) 3.4(3) 4.8(4) 3.5(3) 3.7(3) 7.2(5) 6.6(4) 4.5(5) 5.4(5)
c3 c4 c5 C6 c7 C8 c9 Cl0 c20 c21 c22 C23 C24 C25 C26 C27 C28 c29
0.184(2) 0.294(l) 0.444(2) 0.510(2) 0.665(2) 0.856(2) 0.886(2) 0.832(2) 1.047(2) 1.106(2) 1.161(2) 1.062(2) 0.926(2) 0.859(2) 0.784(2) 0.574(3) 0.489(2) 0.540(2)
(30403)”
Y 0.309(l) 0.098(l) 0.0810(g) -0.031(1) -0.064(l) 0.013(l) 0.129(l) 0.219(l) 0.382(l) 0.435(l) 0.535 (1) 0.739(2) 0.844 ( 1) 0.914(2) 0.873(2) 0.807(2) 0.748(2) 0.683(l)
* 0.571(l) 0.606( 1) 0.6083(g) 0.694 (1) 0.685(l) 0.659 ( 1) 0.633( 1) 0.532(l) 0.236(l) 0.129(l) 0.119(l) 0.113(2) 0.114(l) O.Oll(2) - -0.028(a) 0.027(2) 0.117(2) 0.212(l)
R(A2) 5.2(5) 4.9(4) 4.3(4) 5.9(5) 6.7(6) 7.9(7) 7.7(7) 5.3(5) 7.2(6) 9.1(7) 9.6(7) 10.8(8) 9.2(7) 11.0(8) 12.0(8) 18(l) 12.6(g) 9.7(7)
“Anisotropically refined atoms are given in the form of the isotropic equivalent displacement parameter defined as: (4/3)x[aBxB(l,l)+b2xB(2,2)+c2xB(3,3)+ab(cos y)xB(1,2)+ac(cos /?)xB(1,3)+bc(cos ooxE(2,3)1.
TABLE 4 Bond lengths (A) in di-MACROSPIRO
(30403)
Atom 1
Atom 2
Distance”
Atom 1
Atom 2
Distance”
Pl Pl Pl Pl P2 P2 P2 P2 01 01 02 02 03 03 04 04 Nl Nl N2 N2 N3 N3
Nl N2 N4 N5 Cl1 Cl2 N2 N3 c3 c4 C7 C8 c22 C23 C26 C27 Pl P3 Pl P2 P2 P3
1.60( 1) 1.62(l) 1.63(l) 1.65(l) 2.038(5) 2.009(8) 1.542(9) 1.57(l) 1.44(2) 1.46(l) 1.43(3) 1.43(3) 1.49(2) 1.32(3) 1.55(2) 1.24(4) 1.60( 1) 1.58( 1) 1.62(l) 1.542(9) 1.57(l) 1.63(l)
N4 N4 N5 N5 N6 N6 N7 N7 Cl Cl c2 c2 c3 c3 c4 c4 c5 c5 C6 C6 c7 c7
Pl Cl Pl Cl0 P3 c20 P3 c29 N4 c2 Cl c3 01 c2 01 c5 c4 C6 c5 c7 02 C6
1.63(l) 1.47(3) 1.65(l) 1.44(2) 1.67(2) 1.45(2) 1.65(2) 1.44(2) 1.47(3) 1.52(3) 1.52(3) 1.53(2) 1.44(2) 1.53(2) 1.46(l) 1.47(2) 1.47(2) 1.55(2) 1.55(2) 1.47(2) 1.43(3) 1.47(2)
C8 C8 c9 c9 Cl0 Cl0 c20 c20 c21 c21 c22 c22 C23
02 c9 C8 Cl0 N5 c9 N6 c21 c20 c22 03 c21 03
1.43(3) 1.51(3) 1.51(3) 1.53(3) 1.44(2) 1.53(3) 1.45(2) 1.50(2) 1.50(2) 1.51(3) 1.49(2) 1.51(3) 1.32(3)
C23 C24 C24 C25 C25 C26 C26 C27 c27 C28 C28 c29 c29
C24 C23 C25 C24 C26 04 C25 04 C28 C27 c29 N7 C28
1.53(2) 1.53(2) 1.54(3) 1.54(3) 1.32(4) 1.55(2) 1.32(4) 1.24(4) 1.50(3) 1.50(3) 1.38(3) 1.44(2) 1.38(3)
“Numbers in parentheses are estimated standard deviations in the least significant digits.
dispersion effects from Cromer and Liberman [ 161. Details of the refinement are summarized in Table 2. Both calculations with SDP [ 171 and illustrations with ORTEP [ 181 softwares were performed on a VAX 11730 computer.
72 TABLE 5 Valence angles (deg) in di-MACROSPIRO
(30403)
Atom 1
Atom 2
Atom 3
Angle”
Atom 1
Atom 2
Atom 3
Angle”
Nl Nl Nl N2 N2 N4 Cl1 Cl1 Cl1 Cl2 Cl2 N2 c3 c7 c22 C26 Pl Pl P2 Pl Pl P3
Pl Pl Pl Pl Pl Pl P2 P2 P2 P2 P2 P2 01 02 03 04 Nl N2 N3 N4 N5 N6
N2 N4 N5 N4 N5 N5 Cl2 N2 N3 N2 N3 N3 c4 C8 C23 C27 P3 P2 P3 Cl Cl0 c20
112.9(5) 115.5(6) 106.3(6) 106.4(6) 113.1(5) 102.4(6) 98.5(3) 107.7(3) 108.1(4) 110.6(5) 107.4(4) 122.1(6) 112(2) 113(l) 114(2) 124(2) 128.3(7) 121.7(7) 120.8(6) 123.1(8) 120.8(g) 127(l)
P3 N4 Cl 01 01 c4 c5 02 02 C8 N5 N6 c20 03 03 C23 C24 04 04 C27 N7
N7 Cl c2 c3 c4 c5 C6 c7 C8 c9 Cl0 c20 c21 c22 C23 C24 C25 C26 C27 C28 c29
c29 c2 c3 c2 c5 C6 c7 C6 c9 Cl0 c9 c21 c22 c21 C24 C25 C26 C25 C28 c29 C28
122(l) 113(2) 114(2) 108(2) 114(2) 111(l) 113(l) llO(2) 109(l) 115(2) 113(l) llO(2) 116(2) 105(2) ill(2) 119(2) 122(2) 113(2) 116(2) 123(2) 120(2)
“Numbers in parentheses are estimated standard deviations in the least significant digits.
Crystal and molecular structure of di-MACROSPIRO (30403) As mentioned above, data were collected at 293 K. Final positions and equivalent isotropic thermal parameters are given in Table 3 and bond lengths and angles in di-MACROSPIRO 30403 are given in Tables 4 and 5, respectively. Perspective views of di-MACROSPIRO (30403) are presented in Figs. 1 and 2. Crystal and molecular structure of di-MEGASPIRO (3020203) X-Ray data for di-MEGASPIRO 3020203 were collected at 123 K. Perspective views of di-MEGASPIRO (3020203 ) are presented on Figs. 3 and 4. Final positions and equivalent isotropic thermal parameters are given in Table 6. Bond lengths and valence angles are gathered in Tables 7 and 8, respectively.
Fig. 4. Perspective view of di-MEGASPIRO figure.
TABLE
(3020203)
with N,P, ring into the plane of the
6
Final positions and equivalent isotropic thermal parameters of di-MEGASPIRO Atom
x
Y
z
B(A2)
Atom
x
Cl1 Cl2 Pl
0.6538(2) 0.3149(2)
0.5977(l) 0.4609(l)
0.3724(l)
2.56(4)
c3
0.6138(l) 0.8291(l)
2.65(4) 1.37(3)
c4
0.4371(2) 0.4453(2)
0.3857(l) 0.3842(l)
0.3010(2) 0.9589(6) 0.6482(8)
0.7184(l) 0.9790(4) 0.8499(6)
0.5003(l) 0.2816(l)
1.42(3) 1.42(3)
0.7621(4) 0.8290(8)
2.9(l) 7.7(3)
0.2962(5) 0.4127(5)
0.7838(4) 0.7798(3)
05 06 Nl
0.0632(5) -0.2039(5) 0.4750(6)
0.7182(4) 0.6312(4) 0.7139(4)
0.7377(3) 0.0244(3) -0.0045(3)
2.4(l) 2.0(l) 2.2(l)
0.0714(3)
2.2(l)
0.4908(4)
1.7(l)
N2 N3 N4
0.3492(6) 0.3448(6) 0.6269(6)
0.8184(4) 0.6113(4) 0.9397(4)
0.3353(6) 0.3877(6) 0.1033(6) 0.7856(8) 0.9337(8)
0.8635(4) 0.7775(4) 0.6595(4) 0.9323(6) 1.0428(6)
1.6(l) 1.9(l) 1.9(l) 1.9(l)
Cl4 Cl5
N5 N6 N7 Cl c2
0.3939(4) 0.2830(4) 0.5660(4) 0.5759(4) 0.2145(4) 0.2125(4) 0.5542(5) 0.6336(5)
1.7(l) 1.9(l) 2.4(2) 2.6(2)
Cl8 Cl9 c20
P2 P3 01 02 03 04
C5.4 C5n C6 c7 C8 c9 Cl0 Cl1 Cl2 Cl3
Cl6 Cl7
(3020203
)”
Y
z
BW)
0.9426(8)
1.0704(5)
0.7414(5)
2.2(2)
0.915(l) 0.724(2)
0.9755(7) 0.861(l)
0.8484(6) 0.778(l)
4.5(2) 2.8(4)
0.819(2) 0.521(l)
0.882(l) 0.7410(7)
0.853(l) 0.8025(7)
3.4(4) 3.8(2)
0.3732(g) 0.1233(9)
0.7021(6) 0.7317(7)
0.7135(5) 0.6787(6)
2.7(2) 3.3(2)
0.0892(g)
0.7000(6)
0.1520(8) 0.5685(8) 0.6221(S)
0.8029(6) 0.8442(5) 0.9167(6)
0.5665(5) 0.5439(5) 0.2503(5)
2.8(2) 2.3(2) 2.0(2)
0.5862(8) 0.3306(g) 0.1532(8) -0.1086(8)
0.8449(6) 0.8516(6) 0.7775(5) 0.6528(6)
0.1943(5) 0.0817(5) 0.0119(5)
2.2(2) 2.2(2) 2.6(2)
-0.1932(8) -0.2901(8) -0.1844(8) -0.0259(g)
0.5686(S) 0.5556(6) 0.5033(5) 0.5928(6)
-0.0539(5) -0.0638(5) -0.0266(5) 0.1104(5) 0.1531(5) 0.2430(5)
2.4(2) 2.5(2) 2.3(2) 2.4(2) 2.1(2) 2.4(2)
“Anisotropically refined atoms are given in the form of the isotropic equivalent displacement parameter defined as: (4/3)~[a2xB(l,l)+b2xB(2,2)+c2xB(3,3)+ab(cos y)~B(l,2)+ac(cos P)~B(1,3)+bc(cos (~)xB(2,3)1.
74 TABLE 7 Bond lengths (A) in di-MEGASPIRO (3020203) Atom 1
Atom 2
Distance*
Atom 1
Atom 2
Distance”
Pl Pl Pl Pl P2 P2 P2 P2 P3 P3 P3 P3 01 01 02 02 02 03 03 04 04
Cl1 Cl2 Nl N3 Nl N2 N4 N5 N2 N3 N6 N7 c3 c4 C5n C5.4 C6 c7 C8 Cl3 Cl4
2.038(3) 2.027(2) 1.558(5) 1.568(6) 1.625 (6) 1.595(6) 1.637(4) 1.650(6) 1.595(5) 1.624(7) 1.643(6) 1.639(6) 1.42(2) 1.42(l) 1.38(2) 1.13(2) 1.41(2) 1.45(2) 1.427(9) 1.425(7) 1.43(2)
05 06 06 N4 N5 N6 N7 Cl c2 c4 c4 C6 C8 c9 Cl1 05 Cl2 Cl4 Cl6 Cl8 Cl9
Cl6 Cl7 Cl8 Cl Cl0 Cl1 c20 c2 c3
1.420(7) 1.432(S) 1.44(l) 1.48(l) 1.473(S) 1.460(7) 1.48( 1) 1.519(S) 1.49(l) 1.72(l) 1.32(2) 1.50(2) 1.52(l) 1.51(l) 1.53(l) 1.44(l) 1.512(9) 1.488(S) 1.50(l) 1.53(l) 1.530(7)
C5.4 C5n c7 c9 Cl0 Cl2 Cl5 Cl3 Cl5 Cl7 Cl9 c20
“Numbers in parentheses are estimated standard deviations in the least significant digits.
Remarks about intramolecular contacts in both title molecules Molecular structures of mono-SPIRO derivatives commonly exhibit one N,H bond pointing towards the inside of the loop (and being more precisely into the average plane of this loop) when the second NP-H bond points outside. This observation was analyzed in terms of intramolecular hydrogen bonds (IHB) which then exist only into one half of the loop between N, and the closest 0, atom. In such mono-SPIRO chemicals, distances between ( N1,O1) and (O,,O,) are equal to 2.90 + 0.05 A when the distance between N2 and 0, (no IHB here) is larger and equal to 3.50 -t 0.05 A. Figures 1 and 3 show that the situation looks rather different in di-SPIRO compounds. In di-MACROSPIRO (30403) H,N4, H,N, and H,N, point towards the inside of the corresponding loop whilst H,N, appears to be quasiperpendicular to the average plane of the loop. Actually, some IHB do exist between N, and O3 (d( Ng.. . OS_)= 2.82 A, 13(03,H1N6,Ns) = 96.2 o ), between N, and 0, (d(N,... 0,) = 2,88 A, 0( O,,H,N,,N,) = 110.5” ) and between N, and 0, (d(N,*.. 0,) =2.87 A, 8(04,H1N7,N7) = 112.2” ). Conversely, there do not exist any significant IHB between N4 and 0, (d(N,* - ~0,) =3.44 A,
75 TABLE 8 Valence angles (deg) in di-MEGASPIRO Atom 1
Atom 2
Atom 3
Cl1
Pl Pl
(3020203)
Angle”
Atom 1
Atom 2
Atom 3
Angle”
Cl1 Cl2
Pl
Cl2
Pl
Nl
Pl
Nl
P2
Nl
P2
Nl
P2
Cl2 Nl N3 Nl N3 N3 N2 N4 N5
113.7(3)
02
N2
P2
N4
116.5(4)
02
C5B C6
c4 c7
N2
P2
N5
105.5(4)
03
c7
C6
114.0(9) 109.5 (5)
N4
P2
N5
C8
c9
114.7(7)
P3
N3
100.6(3) 112.1(4)
03
N2
C8
c9
Cl0
114.3(5)
N2
P3
108.6(3)
N5
Cl0
c9
115.2(7)
N2
P3 P3
N6 N7
115.4(3)
N6
Cl1
Cl2
112.5(6)
N6
Cl1 04
Cl2
Cl3
113.7(5)
04
Cl3 Cl4
Cl2 Cl5
114.3(6) 109.7(5)
05 05
Cl5 Cl6
Cl4
110.5(6)
06
Cl7
Cl7 Cl6
llLO(6) 109.4(5)
06 N7
Cl8 c20
Cl1
N3 N3 N6 c3 C5B c7 Cl3 Cl8 Cl5
Pl
98.9(l)
Cl7
06
N4
Cl
Cl8 c2
112.6(5)
108.9(2) 10&l(2)
Cl
c2
c3
114.7(6)
10&O(2)
01
c3
c2
109.1(6)
109.0(2)
01
c4
C5.4
94.7(7)
121.6(3)
01
c4
C5B
126.4(g)
113.6(3)
C5.4 02
c4
106.5(3)
C5*
C5B c4
110.1(9)
P3
N7
114.3(3) 105.7(3)
P3 01
N7 c4
100.6(3) 114.2(6)
02
C6
03 04
C8 Cl4
129(2) 112.1(5)
Cl9
c20
05
Cl6
112.6(5) 114.4(6) 111.1(5)
110.1(6)
42.2(9) 121.0(9)
Cl9
113.7(6)
Cl9
112.9(6)
“Numbers in parentheses are estimated standard deviations in the least significant digits.
t9(O,,H,N,,N,) = 76.0’ ). Thus, the average distance between nitrogen and oxygen atoms involved in IHB is equal to 2.86 +-0.04 A when the distance between N, and 0, atoms not involved in IHB is equal to 3.44 A (i.e. very similar to the values in mono-SPIRO derivatives). In contrast, intramolecular contacts between-pairs of oxygen atoms-in both loops are quite different (d(O,***0,)=5.4_0 A, d(O,**.0,)=3.84 A) both among themselves and from the 2.90 ? 0.05 A value in mono-SPIRO parents. The same features are observed in di-MEGASPIRO (3020203). Indeed, some IHB do exist between N6 and 0, (d(N,. *-0,) = 2.88 A, 8(04,H1N6,N6) =124.2”), between N, and O3 (d(N5**s03)=3.00 A, 0(O,,H,N,,N,)=93.7”) and between N, and OS (d(N7***06)=2.97 A, B(O,,H,N,,N,) = 122.3” ). Conversely, there do not exist any significant IHB between N, and 0, (d(N,**. 0,) =3.52 A, @O,,H,N,,N,) =76.0” ), between N, and O5 (d(N,... 0,) = 3.60 A, 0( 05,H1N6,Ns) = 164.2 o ) and between N, and O5 (d(N,.** 0,) = 3.58 A, 8( O,,H,N,,N,) = 166.0” ). Thus, the average
76
distance between nitrogen and oxygen atoms involved in IHB is equal to 2.95 +-0.05 A when the average distance between N and 0 atoms not involved in IHB is equal to 3.57? 0.03 A. Intramolecular contacts between oxygen atoms of a given loop in di-MEGASPIRO 3020203 are d(Oi-..02)=3.30 A, d(02-..03)=2.89 A, d(O,--- 05)=2.86 A and d(O,.** 0,) =2.90 A. Then, their average value is about the same here as in mono-SPIRO derivatives. Incidentally, 0, and 0, atoms are almost equidistant from (N4,N5) and (N,,N,) pairs (d(0,.-- N4) =4.50 A, d(02-.-N5) =4.38 pi, d(05.-.N6) =3.60 A, d(0, ..*N,)=3.58&. CONCLUSIONS
Aminolysis of N3P3C16 by dioxodiamines and trioxodiamines under suitable experimental conditions yields di-MACROSPIRO and di-MEGASPIRO species which constitute new di-macrocyclic monocyclophosphazenic architectures. X-Ray structures of di-SPIRO derivatives from 4,9-dioxadodecane-1,12diamine and from 4,7,10-trioxatridecane-1,13diamine reveal two 15- and 16membered loops, respectively, grafted onto the same N3P3 ring. In both cases, the two loops are highly unsymmetrical, mainly about the size of their coordination site polyhedra. Thus it may be expected that such molecules will be capable of hosting two different guests, leading to new materials within the field of conductivity. REFERENCES 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
P. Castera, J.-P. Faucher, M. Granier and J.-F. Labarre, Phosphorus Sulfur, 32 (1987) 37. P. Castera, J.-P. Faucher, J.-F. Labarre and B. Perly, J. Mol. Struct., 160 (1987) 365. P. Castera, 195.J.-P. Faucher, M. Graffeuil and J.-F. Labarre, J. Mol. Struct., 176 (1988) 295. R. Enjalbert, J. Galy, P. Castera and J.-F. Labarre, Acta Crystallogr., Sect. C, 44 (1988) 1813. A. El Bakili, P. Castera, J.-P. Faucher, F. Sournies and J.-F. Labarre, J. Mol. Struct., 195 (1989) 21. R. Enjalbert, J. Galy, A. El Bakili, P. Castera, J.-P. Faucher, F. Sournies and J.-F. Labarre, J. Mol. Struct., 196 (1989) 207. T.S. Cameron, A. Linden, A. El Bakili, P. Castera, J.-P. Faucher, M. Graffeuil, F. Sournies and J.-F. Labarre, J. Mol. Struct., 212 (1989) 281. F. Sournies, A. El Bakili, J.-F. Labarre and B. Perly, J. Mol. Struct., 196 (1989) 201. T.S. Cameron, A. Linden, F. Sournies, A. El Bakili and J.-F. Labarre, J. Mol. Struct., 197 (1989) 41. J. Jaud, F. Sournies and J-F. Labarre, J. Mol. Struct., 212 (1989) 305. J.-F. Labarre, Top. Curr. Chem., 129 (1985) 173 and references cited therein. J.-F. Labarre, P. Castera, J.-P. Faucher andF. Sournies, Fr. Pat. No. 89-01782, Feb. 10,1989. R. Garelli, B. Zanin and J.-F. Labarre, Inorg. Chim. Acta, in press. N. El Murr, R. Lahana, J.-F. Labarre and J.-P. Declercq, J. Mol. Struct., 117 (1984) 73. D.T. Cromer and J.T. Waber, International Tables for X-Ray Crystallography, Vol. IV, Kynoch Press, Birmingham, U.K., 1974, Table 2.2A.
16 17 18
D.T. Cromer and D. Liberman, International Tables for X-Ray Crystallography, Vol. IV, Kynoch Press, Birmingham, U.K., 1974, Table 2.3.1. B.A. Frenz, Structure Determination Package, College Station, TX 77840, U.S.A. andEnrafNonius, Debt, The Netherlands, 1985. C.K. Johnson, Ortep II, Report ORNL-5138, Oak Ridge National Laboratory, TN, U.S.A., 1976.
220 (1990) 63-77 B.V., Amsterdam - Printed
63
Structure,
Elsevier Science Publishers
in The Netherlands
AN ANSWER TO THE SPIRO VERSUS ANSA DILEMMA IN CYCLOPHOSPHAZENES Part XIII*. Synthesis and crystal structure of the first diMACROSPIRO and di-MEGASPIRO species from di- and trioxodiamines FRANCOIS SOURNIES, LABARRE** CNRS, Laboratoire Toulouse (France)
ABDELAZIZ
Structure
EL BAKILI, BRUNO ZANIN and JEAN-FRANCOIS
et Vie, FacultP de Pharmacie,
35, rue des Maraichers,
31400
JOEL JAUD Laboratoire
de Chimie de Coordination,
205, route de Narbonne,
31400 Toulouse (France)
(Received 30 May 1989)
ABSTRACT Aminolysis of N,P,Cl, by dioxodiamines and trioxodiamines in suitable conditions yields diMACROSPIRO and di-MEGASPIRO species which constitute new di-macrocyclic monocyclophosphazenic architectures. X-Ray structures of di-SPIRO derivatives from 4,9-dioxadodecane1,12-diamine and from 4,7,10-trioxatridecane-1,13-diamine reveal two highly unsymmetrical 15 and 16.membered loops, respectively, grafted on the same N,P, ring.
INTRODUCTION
Reactions of N3P3C16with oxodiamines such as the 3-oxapentane-l,&diamine (coded as 202)) the 3,6-dioxaoctane-l&diamine (20202), the 4,7-dioxadecane-l,lO-diamine (30203)) the 4,9-dioxadodecane-1,12diamine (30403 ) and the 4,7,10-trioxatridecane-1,13-diamine (3020203) have been investigated in the very recent past in our laboratory with the aim of designing cyclophosphazenic two-ring bridged assembly structures (coded as Barrelanes and cousins [ 1]) which would display a high solubility in common organic solvents and then which could be used for the synthesis of one-dimensional materials for further applications. Actually, these oxodiamines lead surprisingly to monocyclophosphazenic species in which the oxodiamino ligand is grafted either as a SPIRO loop onto one P atom of the N3P3 ring or as an ANSA arch onto two P atoms of the ring. Syntheses are highly stereoselective and even stereospecific in some cases and *For Part XII see ref. 8. **Author to whom correspondence
OOZZ-2860/90/$03.50
should be addressed.
0 1990 Elsevier Science Publishers
B.V.
64
whether the SPIRO or ANSA configuration is obtained depends very much on the solvent used. For example, reaction of 202 with N3PJ& in acetonitrile quantitatively yields the ANSA 202 derivative [2-41, reaction of 20202, 30203 and 30403 in THF lead to the MACRO-SPIRO moieties [ 5-71 while MACRO-ANSA isomers are obtained by using a toluene/Na,CO, interface process [ 5-71. Similarly, reaction of 3020203 with N3P3C& either gives the MEGA-SPIRO species [8-lo] or its MEGA-ANSA isomer [8] depending on experimental conditions. It must be pointed out that the whole structures we just mentioned are either MONO-SPIRO or MONO-ANSA compounds, that is molecules in which one SPIRO loop or one ANSA arch is grafted onto the N3P3 ring. Moreover, these amazing macrocyclic architectures are very major products in every case, the expected two-ring bridged assembly structures just being observed from time to time as very minor side-products. In other words, the synthesis of barrelane-like dicyclophosphazenic species constitutes a challenge waiting to be taken up. The present paper reports on the synthesis and crystal structure of some DISPIRO derivatives from oxodiamines which were obtained by a concerted use of experimental conditions described above for synthesizing the MONO-SPIRO compounds from oxodiamines and of synthetic procedures which had been found to be very successful for obtaining POLY-SPIRO entities from nonoxygenated diamines (according to BASIC rules) [ 111. EXPERIMENTAL
Preliminary remarks The synthesis of MONO-SPIRO compounds proceeds cleanly, as mentioned above, upon reaction of oxodiamines on N3P3C16in (1: 1) stoichiometric conditions and by using a toluene/Na$O, interface process. It could be expected that the corresponding DI-SPIRO moieties would be obtained in the same way when working in (2 : 1) conditions. Actually, this is not the case at all; a 100% excess of oxodiamine with respect to the stoichiometry for the synthesis of MONO-SPIRO derivatives, (i) yields stereospecifically the MONO-SPIRO entity in the case of 30203 (Table 1) and (ii) reveals new complex molecular structures as major derivatives (in addition to the expected MONO-SPIRO one as a minor by-product) in the case of 30403 [ 12,131. It was therefore decided to re-investigate the nature of solvent(s) which would lead to the production of DI-SPIRO species. Despite the severe discrepancies noticed regarding the chemical behaviour of dioxodiamines and of nonoxygenated diamines versus N3P3C16,the production was attempted of DISPIRO derivatives from the former by using the petroleum-ether/dichloromethane (7 : 3) mixture (solvent S) which had been so efficient for the synthesis of the DI-SPIRO cousins from the latter [ 141. Under such conditions, the DI-SPIRO compounds can be obtained from ox-
65
TABLE 1 Synthetic pathways for producing di-MACROSPIRO and di-MEGASPIRO compounds
TOLUENE-WATER _____F
N3P3C’6
mono-MACROSPIRO
30203
TO~~~~~,--~~:~OS~R~~~203 (whatever
stoichiometry
CASE
(yield 100%)
(yield
loos/.)
is)
OF THE
OXODIAMINE
30203
TOLUENE-WATER N3P3Clg
-w
mono-MACROSPIRO
S:L;E;x
SOLVENTS
(yield 50%)
CASE
OF THE
x
1
(yield 40%)
2:1
di-MACROSIPIRO
OXODIAMINE
30403
30403
(yield 60%)
30403
TOLUENE-WATER N3P3C’6
__
CASE
mono-MEGASPIRO
OF THE
OXODIAMINE
3020203
(yield 90%)
3020203
odiamines (i) either from their MONO-SPIRO parents by working in solvent S (Table l), or (ii) from N3P3C16itself (only for 30403, Table 1) but with a rather poor yield in this case. Table 1 gathers the different pathways which can be used to obtain DI-SPIRO compounds from oxodiamines and it may be noticed that chemical processes run “accordingly or not” to the rules of the BASIC chemical game (the solvent S is a common solvent for the synthesis of BASIC systems when the toluene/ water interface process is not ) .
66
Synthesis of di-MACROSPIRO (30403) The synthesis of the title compound may run in solvent S according to the pathway (Table 1) lN,P,C& + 5 (30403) =>di-MACROSPIRO
(30403)
+ (30403.2 HCl)
A large excess of the dioxodiamine is then needed for making the reaction complete. 14.74 g of (30403) in solution in 500 ml of solvent S were added in a single operation to a solution of 5 g N,P,Cl, in 1000 ml S. The trioxodiamine dihydrochloride precipitates immediately and in time forms a waxy deposit on the walls of the vessel. The reaction takes 24 h and was considered complete when the 31PNMR singlet of N3P3C16at 20.09 ppm had disappeared. The clear organic phase was then poured off and the solvent was removed in vacua at 25’ C to give a light yellow syrup (60% yield) containing about 90% of the diMACROSPIRO (30403) derivative and 10% of its mono-MACROSPIRO parent. The major expected di-MACROSPIRO compound was separated from the minor mono-MACROSPIRO moiety through a single SiO, column chromatography using acetonitrile as the eluant (Rf=0.60 and 0.90, respectively, for the di-MACROSPIRO and mono-MACROSPIRO derivatives). Pure diMACROSPIRO (30403) appears as a viscous liquid owing to its clathration with solvents which were used. Stirring for one night with n-heptane gave a white powder which crystallized in Ccl, (final yield 50%) F = 107 oC ) . The 31PNMR spectrum, as recorded on Bruker AC 200 equipment, in CDC13 reveals the P (MACROSPIRO) doublet centred on 13.37 ppm and the P (Cl,) triplet centred on 24.58 ppm, “Jpp = 48.7 Hz. The DC1 mass spectrum was recorded on a NERMAG RlOlO-H quadrupole mass spectrometer. The molecular ion MH+ is correctly observed at m/z 610 with a satellite distribution confirming the presence of two chlorine atoms in the molecule. Synthesis of di-MEGASPIRO (3020203) In toluene/water interface the synthesis of the title derivative may run according to the pathway (Table 1) 1 N3 P3Cls + 5.25 (3020203) *di-MEGASPIRO
(3020203)
+ (3020203.2
HCl)
A large excess of the trioxodiamine is then needed for making the reaction complete. 33.26 g (3020203) dissolved in 500 ml solvent S were added in one operation to a solution of 10 g N,P,Cl, in 1000 ml S. The trioxodiamine dihydrochloride precipitates immediately and in time forms a waxy deposit on the walls of the vessel. The reaction takes 24 h and was considered complete when
67
the 31P NMR singlet of N3P3C16at 20.09 ppm had disappeared. The clear organic phase was then poured off and the solvent was removed in vacua at 25” C to give a light yellow syrup (51% yield) containing about 80% of the di-MEGASPIRO (3020203) derivative and 20% of its mono-MEGASPIRO parent. The major expected di-MEGASPIRO compound was separated from the minor mono-MEGASPIRO moiety through a single SiOZ column chromatography using a (7 : 3 ) mixture of dichloromethane and 2-propanol as the eluant t&=0.56 and 0.27 for the DISPIRO and MONOSPIRO derivatives, respectively ). Pure di-MEGASPIRO (3020203 ) appears as a viscous liquid owing to its clathration with solvents which were used. Stirring for one night with nheptane gave a white powder which crystallized in Ccl, (final yield 20%, F=95”C). The 31PNMR spectrum, as recorded on Bruker AC 200 equipment, in CDC& reveals the P (MEGASPIRO ) doublet centred on 13.26 ppm and the P (CL) triplet centred on 24.06 ppm, ‘Jpp = 48.7 Hz. The EI mass spectrum was recorded on a NERMAG RlOlO-H quadrupole mass spectrometer. The molecular ion M+ is correctly observed at m/z 642 with a satellite distribution confirming the presence of two chlorine atoms in the molecule. The fragmentation pattern displays the classical “festooned” aspect which characterizes the mass spectrum of any SPIRO cyclophosphazene. Such a festooned look is due to successive losses of NH (m/z 15)) CH, (m/z 14) and 0 (m/z 16), links which prove that the two SPIRO loops are actually losing these links “pearl per pearl” upon electron impact. X-RAY STUDY
General remark-s In both cases studied below, a transparent colourless block has been chosen for data collection using an Enraf-Nonius CAD4 diffractometer. The angular coordinates of 25 hkl reflections were centred and least-squares refined to give the lattice parameters (Table 2). Details of data collection for the two compounds are reported in Table 2. Lorentz and polarization corrections were applied. In view of the low values of absorption coefficients, no absorption corrections were then performed. The structure of di-MACROSPIRO (30403 ) (coded as DS 30403 ) (Figs. 1, 2) was measured at room temperature (293 K) and a noticeable wobbling of several atoms in the molecule was observed, thermal parameters of some of the carbon and oxygen atoms at the “outer” ends of the macrocyclic loops being very large. Then, the structure of di-MEGASPIRO (3020203 ) (coded as DS 3020203) was recorded at 123 K with the aim of freezing any eventual wobbling. Actually, this attempt at the production of a well-localized structure at low temperature was not successful. Indeed, a substantial agitation remains at
68 TABLE 2 Physical properties and parameters for data collection and refinement DS 30403 Formula Mol. wt. Cryst. system Sptce group a (A) 5 (A) c (A) (Y (deg) P (deg) Y (deg) v (Aa) z dcalc(g cm-3) d,, (g cmm3) F(OOO) p (MO&X) (cm-‘) Temperature ( ’ C ) 1 (A) Take-off (deg) Detector width (mm) Scan type Scan width (deg) 0 range (deg) No. of measured reflections No. of variables, NV No. of unique refl., NO Agreement R R,
DS 3020203
W’,Q&W-L,
610.4 Triclinic
640.3 Triclinic
Pi
Pi
10.20(9) 12.51(8) 13.48(7) 71.9(2) 78.1(2) 69.0(l) 1518 2 1.330 1.33 648 4.0 20 0.71069 4.0 4x4
8.90(4)
13.55(5) 14.88(8) 111.4(3) 99.9(2) 108.3(4) 1501 n
‘
1.417 1.42 676 4.2 - 150 0.71069 3.2 4x4
ei2e
e/ze
0.8+0.35tan 0 o-22 1958 325 1677
0.85 + 0.35 tan 0 O-25 4968 352 3805
0.087 0.092
0.077 0.088
factors
the level of four atoms (namely Oi, C4, C5 and 02, Fig. 3) at the “outer” end of one of the two loops (notice that the equivalent atoms at the “outer” end of the other loop were perfectly fixed). Attempt at refinement of the structure in the non-centrosymmetric space group Pl were unsuccessful owing to emergence of huge correlations. Thus, it was arbitrarily decided to achieve the refinement in the centro-symmetric space group Pi which revealed the disorder on C, (i.e. two equivalent positions C& and C5n) but not the disorder on O,, C, and 0,. Despite this unsatisfactory conclusion, it was decided to report the structure of di-MEGASPIRO (3020203 ) as it is because it definitely supports the di-MEGASPIRO architecture which had been predicted by NMR and mass spectrometry.
69
C25
Fig. 1. Perspective view of di-MACROSPIRO (30403) quasi-perpendicular to the plane of the figure).
with numbering of atoms (N3P, ring
Fig. 2. Perspective view of di-MACROSPIRO (30403 ) with N,P, ring into the plane of the figure.
The structures were determined using direct methods leading to the localization of chlorine, phosphorus and nitrogen atoms. The carbon, oxygen and hydrogen atoms were located from different Fourier maps. Hydrogen atoms were added to the structure factor calculations as fixed at 0.97 A from their relative attached atoms with a value of 5.5 A” for isotropic temperature factors. Scattering factors were taken from Cromer and Waber [ 151 and anomalous
Cl8
Fig. 3. Perspective quasi-perpendicular
view of di-MEGASPIRO (3020203) to the plane of the figure).
with numbering
of atoms
(N,P,
ring
TABLE 3 Final positions and equivalent isotropic thermal parameters of di-MACROSPIRO Atom
r
Y
.z
S(A2)
Atom
x
Cl1 Cl2 Pl P2 P3 01 02 03 04 Nl N2 N3 N4 N5 N6 N7 Cl c2
0.8186(5) 0.5391(5) 0.6033(4) 0.6817(5) 0.7540(5) 0.224(l) 0.707(l) 1.033(l) 0.663(l) 0.670(l) 0.618(l) 0.757(l) 0.437(l) 0.680(l) 0.921(l) 0.689(l) 0.322(2) 0.180(Z)
0.1508(3) 0.3409(4) 0.3426(3) 0.3016(3) 0.4797(3) 0.2062(7) 0.0337(l) 0.6397(g) 0.8383(g) 0.4484(7) 0.2670(7) 0.3997(S) 0.3821(7) 0.2612(7) 0.467(l) 0.6239(g) 0.408(l) 0.417(l)
0.1952(3) 0.1319(3) 0.4286(3) 0.2314(3) 0.2673(3) 0.5311(6) 0.6828(s) 0.1261(g) 0.0504(g) 0.3794(7) 0.3461(7) 0.1918(7) 0.4741(7) 0.5352(7) 0.271(l) 0.2158(g) 0.411(l) 0.477(l)
6.9(l) 7.7(2) 3.6(l) 4.3(l) 4.7(l) 5.3(3) 4.8(3) 10.0(5) 9.7(5) 4.0(3) 3.4(3) 4.8(4) 3.5(3) 3.7(3) 7.2(5) 6.6(4) 4.5(5) 5.4(5)
c3 c4 c5 C6 c7 C8 c9 Cl0 c20 c21 c22 C23 C24 C25 C26 C27 C28 c29
0.184(2) 0.294(l) 0.444(2) 0.510(2) 0.665(2) 0.856(2) 0.886(2) 0.832(2) 1.047(2) 1.106(2) 1.161(2) 1.062(2) 0.926(2) 0.859(2) 0.784(2) 0.574(3) 0.489(2) 0.540(2)
(30403)”
Y 0.309(l) 0.098(l) 0.0810(g) -0.031(1) -0.064(l) 0.013(l) 0.129(l) 0.219(l) 0.382(l) 0.435(l) 0.535 (1) 0.739(2) 0.844 ( 1) 0.914(2) 0.873(2) 0.807(2) 0.748(2) 0.683(l)
* 0.571(l) 0.606( 1) 0.6083(g) 0.694 (1) 0.685(l) 0.659 ( 1) 0.633( 1) 0.532(l) 0.236(l) 0.129(l) 0.119(l) 0.113(2) 0.114(l) O.Oll(2) - -0.028(a) 0.027(2) 0.117(2) 0.212(l)
R(A2) 5.2(5) 4.9(4) 4.3(4) 5.9(5) 6.7(6) 7.9(7) 7.7(7) 5.3(5) 7.2(6) 9.1(7) 9.6(7) 10.8(8) 9.2(7) 11.0(8) 12.0(8) 18(l) 12.6(g) 9.7(7)
“Anisotropically refined atoms are given in the form of the isotropic equivalent displacement parameter defined as: (4/3)x[aBxB(l,l)+b2xB(2,2)+c2xB(3,3)+ab(cos y)xB(1,2)+ac(cos /?)xB(1,3)+bc(cos ooxE(2,3)1.
TABLE 4 Bond lengths (A) in di-MACROSPIRO
(30403)
Atom 1
Atom 2
Distance”
Atom 1
Atom 2
Distance”
Pl Pl Pl Pl P2 P2 P2 P2 01 01 02 02 03 03 04 04 Nl Nl N2 N2 N3 N3
Nl N2 N4 N5 Cl1 Cl2 N2 N3 c3 c4 C7 C8 c22 C23 C26 C27 Pl P3 Pl P2 P2 P3
1.60( 1) 1.62(l) 1.63(l) 1.65(l) 2.038(5) 2.009(8) 1.542(9) 1.57(l) 1.44(2) 1.46(l) 1.43(3) 1.43(3) 1.49(2) 1.32(3) 1.55(2) 1.24(4) 1.60( 1) 1.58( 1) 1.62(l) 1.542(9) 1.57(l) 1.63(l)
N4 N4 N5 N5 N6 N6 N7 N7 Cl Cl c2 c2 c3 c3 c4 c4 c5 c5 C6 C6 c7 c7
Pl Cl Pl Cl0 P3 c20 P3 c29 N4 c2 Cl c3 01 c2 01 c5 c4 C6 c5 c7 02 C6
1.63(l) 1.47(3) 1.65(l) 1.44(2) 1.67(2) 1.45(2) 1.65(2) 1.44(2) 1.47(3) 1.52(3) 1.52(3) 1.53(2) 1.44(2) 1.53(2) 1.46(l) 1.47(2) 1.47(2) 1.55(2) 1.55(2) 1.47(2) 1.43(3) 1.47(2)
C8 C8 c9 c9 Cl0 Cl0 c20 c20 c21 c21 c22 c22 C23
02 c9 C8 Cl0 N5 c9 N6 c21 c20 c22 03 c21 03
1.43(3) 1.51(3) 1.51(3) 1.53(3) 1.44(2) 1.53(3) 1.45(2) 1.50(2) 1.50(2) 1.51(3) 1.49(2) 1.51(3) 1.32(3)
C23 C24 C24 C25 C25 C26 C26 C27 c27 C28 C28 c29 c29
C24 C23 C25 C24 C26 04 C25 04 C28 C27 c29 N7 C28
1.53(2) 1.53(2) 1.54(3) 1.54(3) 1.32(4) 1.55(2) 1.32(4) 1.24(4) 1.50(3) 1.50(3) 1.38(3) 1.44(2) 1.38(3)
“Numbers in parentheses are estimated standard deviations in the least significant digits.
dispersion effects from Cromer and Liberman [ 161. Details of the refinement are summarized in Table 2. Both calculations with SDP [ 171 and illustrations with ORTEP [ 181 softwares were performed on a VAX 11730 computer.
72 TABLE 5 Valence angles (deg) in di-MACROSPIRO
(30403)
Atom 1
Atom 2
Atom 3
Angle”
Atom 1
Atom 2
Atom 3
Angle”
Nl Nl Nl N2 N2 N4 Cl1 Cl1 Cl1 Cl2 Cl2 N2 c3 c7 c22 C26 Pl Pl P2 Pl Pl P3
Pl Pl Pl Pl Pl Pl P2 P2 P2 P2 P2 P2 01 02 03 04 Nl N2 N3 N4 N5 N6
N2 N4 N5 N4 N5 N5 Cl2 N2 N3 N2 N3 N3 c4 C8 C23 C27 P3 P2 P3 Cl Cl0 c20
112.9(5) 115.5(6) 106.3(6) 106.4(6) 113.1(5) 102.4(6) 98.5(3) 107.7(3) 108.1(4) 110.6(5) 107.4(4) 122.1(6) 112(2) 113(l) 114(2) 124(2) 128.3(7) 121.7(7) 120.8(6) 123.1(8) 120.8(g) 127(l)
P3 N4 Cl 01 01 c4 c5 02 02 C8 N5 N6 c20 03 03 C23 C24 04 04 C27 N7
N7 Cl c2 c3 c4 c5 C6 c7 C8 c9 Cl0 c20 c21 c22 C23 C24 C25 C26 C27 C28 c29
c29 c2 c3 c2 c5 C6 c7 C6 c9 Cl0 c9 c21 c22 c21 C24 C25 C26 C25 C28 c29 C28
122(l) 113(2) 114(2) 108(2) 114(2) 111(l) 113(l) llO(2) 109(l) 115(2) 113(l) llO(2) 116(2) 105(2) ill(2) 119(2) 122(2) 113(2) 116(2) 123(2) 120(2)
“Numbers in parentheses are estimated standard deviations in the least significant digits.
Crystal and molecular structure of di-MACROSPIRO (30403) As mentioned above, data were collected at 293 K. Final positions and equivalent isotropic thermal parameters are given in Table 3 and bond lengths and angles in di-MACROSPIRO 30403 are given in Tables 4 and 5, respectively. Perspective views of di-MACROSPIRO (30403) are presented in Figs. 1 and 2. Crystal and molecular structure of di-MEGASPIRO (3020203) X-Ray data for di-MEGASPIRO 3020203 were collected at 123 K. Perspective views of di-MEGASPIRO (3020203 ) are presented on Figs. 3 and 4. Final positions and equivalent isotropic thermal parameters are given in Table 6. Bond lengths and valence angles are gathered in Tables 7 and 8, respectively.
Fig. 4. Perspective view of di-MEGASPIRO figure.
TABLE
(3020203)
with N,P, ring into the plane of the
6
Final positions and equivalent isotropic thermal parameters of di-MEGASPIRO Atom
x
Y
z
B(A2)
Atom
x
Cl1 Cl2 Pl
0.6538(2) 0.3149(2)
0.5977(l) 0.4609(l)
0.3724(l)
2.56(4)
c3
0.6138(l) 0.8291(l)
2.65(4) 1.37(3)
c4
0.4371(2) 0.4453(2)
0.3857(l) 0.3842(l)
0.3010(2) 0.9589(6) 0.6482(8)
0.7184(l) 0.9790(4) 0.8499(6)
0.5003(l) 0.2816(l)
1.42(3) 1.42(3)
0.7621(4) 0.8290(8)
2.9(l) 7.7(3)
0.2962(5) 0.4127(5)
0.7838(4) 0.7798(3)
05 06 Nl
0.0632(5) -0.2039(5) 0.4750(6)
0.7182(4) 0.6312(4) 0.7139(4)
0.7377(3) 0.0244(3) -0.0045(3)
2.4(l) 2.0(l) 2.2(l)
0.0714(3)
2.2(l)
0.4908(4)
1.7(l)
N2 N3 N4
0.3492(6) 0.3448(6) 0.6269(6)
0.8184(4) 0.6113(4) 0.9397(4)
0.3353(6) 0.3877(6) 0.1033(6) 0.7856(8) 0.9337(8)
0.8635(4) 0.7775(4) 0.6595(4) 0.9323(6) 1.0428(6)
1.6(l) 1.9(l) 1.9(l) 1.9(l)
Cl4 Cl5
N5 N6 N7 Cl c2
0.3939(4) 0.2830(4) 0.5660(4) 0.5759(4) 0.2145(4) 0.2125(4) 0.5542(5) 0.6336(5)
1.7(l) 1.9(l) 2.4(2) 2.6(2)
Cl8 Cl9 c20
P2 P3 01 02 03 04
C5.4 C5n C6 c7 C8 c9 Cl0 Cl1 Cl2 Cl3
Cl6 Cl7
(3020203
)”
Y
z
BW)
0.9426(8)
1.0704(5)
0.7414(5)
2.2(2)
0.915(l) 0.724(2)
0.9755(7) 0.861(l)
0.8484(6) 0.778(l)
4.5(2) 2.8(4)
0.819(2) 0.521(l)
0.882(l) 0.7410(7)
0.853(l) 0.8025(7)
3.4(4) 3.8(2)
0.3732(g) 0.1233(9)
0.7021(6) 0.7317(7)
0.7135(5) 0.6787(6)
2.7(2) 3.3(2)
0.0892(g)
0.7000(6)
0.1520(8) 0.5685(8) 0.6221(S)
0.8029(6) 0.8442(5) 0.9167(6)
0.5665(5) 0.5439(5) 0.2503(5)
2.8(2) 2.3(2) 2.0(2)
0.5862(8) 0.3306(g) 0.1532(8) -0.1086(8)
0.8449(6) 0.8516(6) 0.7775(5) 0.6528(6)
0.1943(5) 0.0817(5) 0.0119(5)
2.2(2) 2.2(2) 2.6(2)
-0.1932(8) -0.2901(8) -0.1844(8) -0.0259(g)
0.5686(S) 0.5556(6) 0.5033(5) 0.5928(6)
-0.0539(5) -0.0638(5) -0.0266(5) 0.1104(5) 0.1531(5) 0.2430(5)
2.4(2) 2.5(2) 2.3(2) 2.4(2) 2.1(2) 2.4(2)
“Anisotropically refined atoms are given in the form of the isotropic equivalent displacement parameter defined as: (4/3)~[a2xB(l,l)+b2xB(2,2)+c2xB(3,3)+ab(cos y)~B(l,2)+ac(cos P)~B(1,3)+bc(cos (~)xB(2,3)1.
74 TABLE 7 Bond lengths (A) in di-MEGASPIRO (3020203) Atom 1
Atom 2
Distance*
Atom 1
Atom 2
Distance”
Pl Pl Pl Pl P2 P2 P2 P2 P3 P3 P3 P3 01 01 02 02 02 03 03 04 04
Cl1 Cl2 Nl N3 Nl N2 N4 N5 N2 N3 N6 N7 c3 c4 C5n C5.4 C6 c7 C8 Cl3 Cl4
2.038(3) 2.027(2) 1.558(5) 1.568(6) 1.625 (6) 1.595(6) 1.637(4) 1.650(6) 1.595(5) 1.624(7) 1.643(6) 1.639(6) 1.42(2) 1.42(l) 1.38(2) 1.13(2) 1.41(2) 1.45(2) 1.427(9) 1.425(7) 1.43(2)
05 06 06 N4 N5 N6 N7 Cl c2 c4 c4 C6 C8 c9 Cl1 05 Cl2 Cl4 Cl6 Cl8 Cl9
Cl6 Cl7 Cl8 Cl Cl0 Cl1 c20 c2 c3
1.420(7) 1.432(S) 1.44(l) 1.48(l) 1.473(S) 1.460(7) 1.48( 1) 1.519(S) 1.49(l) 1.72(l) 1.32(2) 1.50(2) 1.52(l) 1.51(l) 1.53(l) 1.44(l) 1.512(9) 1.488(S) 1.50(l) 1.53(l) 1.530(7)
C5.4 C5n c7 c9 Cl0 Cl2 Cl5 Cl3 Cl5 Cl7 Cl9 c20
“Numbers in parentheses are estimated standard deviations in the least significant digits.
Remarks about intramolecular contacts in both title molecules Molecular structures of mono-SPIRO derivatives commonly exhibit one N,H bond pointing towards the inside of the loop (and being more precisely into the average plane of this loop) when the second NP-H bond points outside. This observation was analyzed in terms of intramolecular hydrogen bonds (IHB) which then exist only into one half of the loop between N, and the closest 0, atom. In such mono-SPIRO chemicals, distances between ( N1,O1) and (O,,O,) are equal to 2.90 + 0.05 A when the distance between N2 and 0, (no IHB here) is larger and equal to 3.50 -t 0.05 A. Figures 1 and 3 show that the situation looks rather different in di-SPIRO compounds. In di-MACROSPIRO (30403) H,N4, H,N, and H,N, point towards the inside of the corresponding loop whilst H,N, appears to be quasiperpendicular to the average plane of the loop. Actually, some IHB do exist between N, and O3 (d( Ng.. . OS_)= 2.82 A, 13(03,H1N6,Ns) = 96.2 o ), between N, and 0, (d(N,... 0,) = 2,88 A, 0( O,,H,N,,N,) = 110.5” ) and between N, and 0, (d(N,*.. 0,) =2.87 A, 8(04,H1N7,N7) = 112.2” ). Conversely, there do not exist any significant IHB between N4 and 0, (d(N,* - ~0,) =3.44 A,
75 TABLE 8 Valence angles (deg) in di-MEGASPIRO Atom 1
Atom 2
Atom 3
Cl1
Pl Pl
(3020203)
Angle”
Atom 1
Atom 2
Atom 3
Angle”
Cl1 Cl2
Pl
Cl2
Pl
Nl
Pl
Nl
P2
Nl
P2
Nl
P2
Cl2 Nl N3 Nl N3 N3 N2 N4 N5
113.7(3)
02
N2
P2
N4
116.5(4)
02
C5B C6
c4 c7
N2
P2
N5
105.5(4)
03
c7
C6
114.0(9) 109.5 (5)
N4
P2
N5
C8
c9
114.7(7)
P3
N3
100.6(3) 112.1(4)
03
N2
C8
c9
Cl0
114.3(5)
N2
P3
108.6(3)
N5
Cl0
c9
115.2(7)
N2
P3 P3
N6 N7
115.4(3)
N6
Cl1
Cl2
112.5(6)
N6
Cl1 04
Cl2
Cl3
113.7(5)
04
Cl3 Cl4
Cl2 Cl5
114.3(6) 109.7(5)
05 05
Cl5 Cl6
Cl4
110.5(6)
06
Cl7
Cl7 Cl6
llLO(6) 109.4(5)
06 N7
Cl8 c20
Cl1
N3 N3 N6 c3 C5B c7 Cl3 Cl8 Cl5
Pl
98.9(l)
Cl7
06
N4
Cl
Cl8 c2
112.6(5)
108.9(2) 10&l(2)
Cl
c2
c3
114.7(6)
10&O(2)
01
c3
c2
109.1(6)
109.0(2)
01
c4
C5.4
94.7(7)
121.6(3)
01
c4
C5B
126.4(g)
113.6(3)
C5.4 02
c4
106.5(3)
C5*
C5B c4
110.1(9)
P3
N7
114.3(3) 105.7(3)
P3 01
N7 c4
100.6(3) 114.2(6)
02
C6
03 04
C8 Cl4
129(2) 112.1(5)
Cl9
c20
05
Cl6
112.6(5) 114.4(6) 111.1(5)
110.1(6)
42.2(9) 121.0(9)
Cl9
113.7(6)
Cl9
112.9(6)
“Numbers in parentheses are estimated standard deviations in the least significant digits.
t9(O,,H,N,,N,) = 76.0’ ). Thus, the average distance between nitrogen and oxygen atoms involved in IHB is equal to 2.86 +-0.04 A when the distance between N, and 0, atoms not involved in IHB is equal to 3.44 A (i.e. very similar to the values in mono-SPIRO derivatives). In contrast, intramolecular contacts between-pairs of oxygen atoms-in both loops are quite different (d(O,***0,)=5.4_0 A, d(O,**.0,)=3.84 A) both among themselves and from the 2.90 ? 0.05 A value in mono-SPIRO parents. The same features are observed in di-MEGASPIRO (3020203). Indeed, some IHB do exist between N6 and 0, (d(N,. *-0,) = 2.88 A, 8(04,H1N6,N6) =124.2”), between N, and O3 (d(N5**s03)=3.00 A, 0(O,,H,N,,N,)=93.7”) and between N, and OS (d(N7***06)=2.97 A, B(O,,H,N,,N,) = 122.3” ). Conversely, there do not exist any significant IHB between N, and 0, (d(N,**. 0,) =3.52 A, @O,,H,N,,N,) =76.0” ), between N, and O5 (d(N,... 0,) = 3.60 A, 0( 05,H1N6,Ns) = 164.2 o ) and between N, and O5 (d(N,.** 0,) = 3.58 A, 8( O,,H,N,,N,) = 166.0” ). Thus, the average
76
distance between nitrogen and oxygen atoms involved in IHB is equal to 2.95 +-0.05 A when the average distance between N and 0 atoms not involved in IHB is equal to 3.57? 0.03 A. Intramolecular contacts between oxygen atoms of a given loop in di-MEGASPIRO 3020203 are d(Oi-..02)=3.30 A, d(02-..03)=2.89 A, d(O,--- 05)=2.86 A and d(O,.** 0,) =2.90 A. Then, their average value is about the same here as in mono-SPIRO derivatives. Incidentally, 0, and 0, atoms are almost equidistant from (N4,N5) and (N,,N,) pairs (d(0,.-- N4) =4.50 A, d(02-.-N5) =4.38 pi, d(05.-.N6) =3.60 A, d(0, ..*N,)=3.58&. CONCLUSIONS
Aminolysis of N3P3C16 by dioxodiamines and trioxodiamines under suitable experimental conditions yields di-MACROSPIRO and di-MEGASPIRO species which constitute new di-macrocyclic monocyclophosphazenic architectures. X-Ray structures of di-SPIRO derivatives from 4,9-dioxadodecane-1,12diamine and from 4,7,10-trioxatridecane-1,13diamine reveal two 15- and 16membered loops, respectively, grafted onto the same N3P3 ring. In both cases, the two loops are highly unsymmetrical, mainly about the size of their coordination site polyhedra. Thus it may be expected that such molecules will be capable of hosting two different guests, leading to new materials within the field of conductivity. REFERENCES 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
P. Castera, J.-P. Faucher, M. Granier and J.-F. Labarre, Phosphorus Sulfur, 32 (1987) 37. P. Castera, J.-P. Faucher, J.-F. Labarre and B. Perly, J. Mol. Struct., 160 (1987) 365. P. Castera, 195.J.-P. Faucher, M. Graffeuil and J.-F. Labarre, J. Mol. Struct., 176 (1988) 295. R. Enjalbert, J. Galy, P. Castera and J.-F. Labarre, Acta Crystallogr., Sect. C, 44 (1988) 1813. A. El Bakili, P. Castera, J.-P. Faucher, F. Sournies and J.-F. Labarre, J. Mol. Struct., 195 (1989) 21. R. Enjalbert, J. Galy, A. El Bakili, P. Castera, J.-P. Faucher, F. Sournies and J.-F. Labarre, J. Mol. Struct., 196 (1989) 207. T.S. Cameron, A. Linden, A. El Bakili, P. Castera, J.-P. Faucher, M. Graffeuil, F. Sournies and J.-F. Labarre, J. Mol. Struct., 212 (1989) 281. F. Sournies, A. El Bakili, J.-F. Labarre and B. Perly, J. Mol. Struct., 196 (1989) 201. T.S. Cameron, A. Linden, F. Sournies, A. El Bakili and J.-F. Labarre, J. Mol. Struct., 197 (1989) 41. J. Jaud, F. Sournies and J-F. Labarre, J. Mol. Struct., 212 (1989) 305. J.-F. Labarre, Top. Curr. Chem., 129 (1985) 173 and references cited therein. J.-F. Labarre, P. Castera, J.-P. Faucher andF. Sournies, Fr. Pat. No. 89-01782, Feb. 10,1989. R. Garelli, B. Zanin and J.-F. Labarre, Inorg. Chim. Acta, in press. N. El Murr, R. Lahana, J.-F. Labarre and J.-P. Declercq, J. Mol. Struct., 117 (1984) 73. D.T. Cromer and J.T. Waber, International Tables for X-Ray Crystallography, Vol. IV, Kynoch Press, Birmingham, U.K., 1974, Table 2.2A.
16 17 18
D.T. Cromer and D. Liberman, International Tables for X-Ray Crystallography, Vol. IV, Kynoch Press, Birmingham, U.K., 1974, Table 2.3.1. B.A. Frenz, Structure Determination Package, College Station, TX 77840, U.S.A. andEnrafNonius, Debt, The Netherlands, 1985. C.K. Johnson, Ortep II, Report ORNL-5138, Oak Ridge National Laboratory, TN, U.S.A., 1976.