An answer to the spiro versus ANSA dilemma in cyclophosphazenes

Journal of Molecrelar Structure, 117 (1984) Elsevier

Science

Publishers

B.V.,

Amsterdam

73--85 - Printed

in The Netherlands

AN ANSWER TO THE SPIRO VERSUS ANSA DILEMMA IN CYCLOPHOSPHAZENES Part V*. The DISPIRO N3P&12 [HN-(CH2)3,4-NH] N3P3 [HN-(CH,),-NH] 3 derivatives

NADA

EL MURR,

ROGER

Laboratolre Structure Toulouse (France) JEAN-PAUL

Vie,

and JEAN-FRANCOIS

Universitg

Paul Sabatrer.

LABARRE**

118

Route

de Narbonne,

31062

DECLERCQ

Luboratoire de Louvain-La-Neuve (Received

et

LAHANA

2 and TRISPIRO

Chmale Physique (Eelgium)

15 November

et

de

Crzstallographze,

UniJersltL

de

Louvain,

1348

1983)

ABSTRACT The reaction tine) In suitable PNHR-containing polymerzation

of N,P,Cl, non-polar DISPIRO

with 1,3-diaminopropane and 1,4-diammobutane (putressolvents allows the synthesis, with a very high yield of the and TRISPIRO derivatives mthout any slgmficant side-

INTRODUCTION

A systematic structural investigation of the products of the reaction of NJP3C16 with large diamines is now in progress in this laboratory with the aim of settling the so-called SPIRO ] l] vs. ANSA [Z] tiemma. Conclusive evidence for a SPIRO structure for N3P3C& [HN-(CH,),-NH] was recently obtained [3] and it was shown that neither any ANSA form nor DISPIRO side-products resulted from the reaction of N3P3C16 with 1,3diaminopropane under stoichiometic conditions. In other words, the reaction of N3P3C16 wrth 1,3-diammopropane leads to a purely SPIRO moiety. In contrast, the reaction of NsPsC16 with 1,4-diaminobutane leads to two compounds: the malor product, N3P3C& [HN-(CH,),-NH], has a SPIRO configuration [4] whereas the side product displays a two-ring bridgedassembly structure 151, this bridged bicychc structure bemg coded as a BIN0 structure. Thus, it could be claimed that the reaction of N3P3C16 with 1,4-diammobutane, under stoichiometic conditions at least, does not lead to any product having an ANSA structure. Thus the SPIRO vs. ANSA *For Part IV, see ref. 21. **Author for correspondence 0022-2860/84/$03.00

0

1984

Elsevier

Science

Publishers

B.V.

dilemma ought to be replaced by the SPIRO vs. BIN0 one, the more so as the balance between SPIRO and BIN0 forms turns in favour of the latter as the length of the diamine increases. The yield of these reactions is high (65% or more) when using non polar solvents in order to minimize the formation of non crystalline resins (cyclolinear and/or cycle-matrix polymers). It is well known that polar solvents (e.g., diethyl ether, DMSO) lead to a proton-abstraction process from the PNIJR groups of the loop, thus promoting polymerization [6, 73. Such polymerization was claimed to be responsible for failure to prepare monomeric DISPIRO and TRISPIRO diamino derivatives of N3P3C16 [S] containing PNlJR groups, in contrast with reaction of N3P3C16 with secondary -NRH, where DISPIRO chemicals could be obtained diamines, HRN-(CH& [9] (no PN_HR groups in the loop; no major polymerization). Thus, it seemed interesting to reinvestigate the reaction of N3P3C16 with primary d&nines in non polar solvents with the aim of preparing PN_HR-containing DISPIRO and TRISPIRO chemicals. The present paper reports on the synthesis and physico-chemical identity of two DISPIRO derivatives, N3P&la [HN-(CH,),-NH] z and NXPBCl, [HN--(CH,),-NH], (hereafter called DISPIRO 3 and DISPIRO 4, respectively) and of the TRISPIRO N3P3[HN--(CH;,)3-NH] 3 coded as TRISPIRO 3). THE

DISPLRO

3 and DISPIRO

4 DERIVATIVES

Synthesis The DISPIRO products were synthesized by following two methods with a (7:3) mixture of n-hexane and CH,Cl, as the solvent: (1) The one-step route in which a mixture of NJPJCle and the suitable diamine (1:4) is allowed to react at room temperature for 4 h (Chivers’ technique [9] ); (2) the two-step route in which the MONOSPIRO derivative is obtained and purified in the first step and then allowed to react with a suitable excess of diamine to lead to the expected DISPIRO chemical. (1:2) ratios of N,P,Cl, and diamine were used in each of these two steps, the diamine grafting the SPIRO loops onto the N3P3 ring and trapping HCl. The resulting samples from these two techniques were found to be identical from their elemental analyses, melting points (DISPIRO 3 and DISPIRO 4 were higher than 280°C (decomposed)) and IR spectra. The yields were about 60%. Thin-layer chromatography gives R, values of 0.68 and 0.66 with CHBOH as eluant and iodine vapour as developer. Mass spectivmetry Spectra were recorded on a RlOlO Ribermag quadrupole mass spectrometer using a direct inlet system. The source temperature was 150°C and

75

electron energy 70 eV. Spectra were analyzed by means of a DEC PDP 8/M computer and stored on a disk. A small sample (~1 pg) was introduced onto the probe, the temperature of which was then gradually increased from ambient temperature to 100°C taking care that neither the electron multipher nor the amplifier were in a saturated condition at any tune. The area under the curves corresponding to the current carned by the selected ions were calculated by the computer. The 70eV electron-impact mass spectrum of DISPIRO 3 (M = 349.95) IS shown in Fig. 1. The molecular ion M” was observed at m/z 349(80.4%) with a set of satellites at m/z 350(14.6%) and 351(51.1%). The intensity ratio of these three peaks indicates the presence of two chlorine atoms in the molecule. One other satellite of M+ was observed at m/z 348(9.1%), correspondmg to the loss of one H atom. One mam fragment&Ion route involves successive losses of lCH,, 2CH2, 3CH2, 3CH2 + 1NH and 3CHz + 2NH (associated with H-transfers) to give maximal peaks at m/z 336(1.30/o), 321(2.9%), 307(3.4%), 291(4.3X) and 276(10.3%). Further consecutive losses of chlorine atoms give peaks at m/z 242(6.0%) and 206(11.3%). The remaining loop of the m/z 276 entity is fragmented in the same way as above: the successive loss of lCH% 2CH2, 3CHz, 3CHz + 1NH and 3CH2 + 2NH (also associated with H-transfers) gives maxunal peaks at m/z 262(5.1%), 249(17-O%), 236(9-l%), 221(18.6%) and 206(11.3%). Further consecutive losses of chlorine atoms give minor peaks at m/z 170(1.8%) and 136(1.8%). Another fragmentation route is observed with peaks at m/z 314(8.8%) and 278(100%), corresponding to the successive loss of one and two chlorine atoms (again associated with H-transfers) from the molecular ion. These two fragments lose in sequence the CH2 and NH parts of their two loops in the same way as described above for M’.

Z

r

1

1u

Fig. 1. Electron-impact (70-eV)

mass spectrum of DISPLRO 3.

76 It is noteworthy that there are some peak overlaps provided by the different routes of fragmentation, which results from the identity of mass (71) for two chlorine atoms and for the [HN-(CH&-NH minus H] block. In the low-mass range, peaks are observed at m/z 57(10.1%), ‘71(11.1%) and 149(6.6%), which correspond to the HN-(CH&, HN-(CH&-N and NjPBN fragments. Moreover, two rather intense peaks are detected at m/z 86(11.7%) and 84(21.1%), which may correspond to the molecular ion of piperazine (provided by a rearrangement of four CH1 groups and of two NH2 groups of the DISPIRO 3 molecule) and to the [piperazine minus 2H] fragment. The 70-eV electron-impact mass spectrum of DISPIRO 4 (M = 378.18) is shown in Fig. 2. The molecular ion MC was observed at m/z 378(39.1%) with a set of satellites at m/z 379(66.7%) and 380(17.4%). One other satellite of M+, at m/z 377(100%), corresponds .tc the loss of one hydrogen atom (base peak). Fragmentation routes are quite similar to the ones detailed above for DISPIRO 3, except that the [MC - 2Cl] peak (which was the base peak (m/z 278) for DISPIRO 3) is not observed at all here. Peaks of Fig. 2 are assigned as follows: M+- 2CH,; m/z 336(4.5%): m/z 364(2,4%): W - ICH,; m/z 350(3.1%): M+ - 4CHz M’3CH,; m/z 322(11.10/o): W - 4CHP; m/z 292(64.6%): M1 - 2CH,; 2NH = M,; m/z 273(15_7%): M1 - lCHz; m/z 264(14.3%): m/z 250(4.1%): M1 - 3CHz; m/z 238(25-S%): M1 - 4CHz; m/z 221(23.0%): Ml - 4CHz - 1NH; m/z 206(24.1%): M1 - 4CH2 - 2NH = Mz; m/z 172 (3.4%): M2 - 1Cl; m/z 135(3.8%): M2 - 2Cl= N3P3. Residual peaks can also be assigned: m/z 342(7.3%): IM’ - 1Cl = M,; m/z 287(6.2%): M3 -4CH,;m/z 271(&O%): M3 - 4CH2 - 1NH; m/z 256(6.9%): M3 - 4CHz - 2NH. Anyhow, fragmentation routes for DISPIRO 3 and DISPIRO 4 are very

r

1

I

1113

l30

160

1%

220

250

280

310

3-a

370

400

fujl

Fig. 2. Electron-impact (7O-eV) mass spectrum of DISPIRO 4.

77

similar to the ones previously described for SPIRO 3, i.e., N3P3CL [HN(CH2)a-NH] [3] and SPIRO 4, i.e., N3PBC14 [HN-(CH,),-NH] [4] _ However, one has to pay attention to the different kinds of base peaks (I= 100%). For these four structures we observe (Fig. 3) that base peaks for SPIRO 4 and DISPIRO 4 correspond to their molecular ions M, whilst the base peaks for SPIRO 3 and DISPIRO 3 correspond to M - loop and M’ - 2C1, respectively. In other words, SPIRO 4 and DISPIRO 4 appear to be more stable upon electron impact than their [HN-(CH2)3-NH] -beanng relatives_ These observations can presumably be related to the relative stability of the four chemicals vs. au moisture: DISPIRO 3 is mdeed the only one of the series which is slowly hydrolyzed at room temperature, OH groups then replacing the “labile” Cl atoms of the structure. In conclusion, mass spectrometry is an adequate tool for controlling the purity of MONOSPIRO and DISPIRO compounds, as was demonstrated previously in the case of other cyclophosphazenes with biological significance [lo]. Moreover, fragmentation routes of the compounds in question provide some information about their relative stability and, consequently, about their chemical behaviour.

cvl *-.--,/y--.,,

<”I (&&--J \‘\

8’ I

,’

‘\ ‘. -._

--___--

_* c-

,,’

Fig 3. Nature of the fragments DISPIRO 3 and DISPIRO 4.

correspondmg

to the base peaks

in SPIRO

3, SPIRO

4,

78

NMR Spec tmscop y The 313 NMR spectra of DISPIRO 3 and DISPIRO 4 were recorded on a Brucker WII90 instrument (solvent: CD&12; 85% I&PO4 as standard). The doublets at 13.6, 11.91 ppm and 17.19, 15.90 ppm, respectively, correspond to the loop-bearing phosphorus atoms and the triplets at 22.63, 21.39, 20.25 ppm and 25.66, 24.33, 22.92 ppm are attributed to the PC& moieties Table 1 shows 31P NMR data for MONOSPIRO and DISPIRO relatives. J pp - values are found to be identical for SPIRO 4 and DISPIRO 4, whereas they differ when passing from SPIRO 3 to DISPIRO 3, the NMR behaviour of DISPIRO 3 bemg closer to tha, of SPIRO 4 and DISPIRO 4 than to that of SPIRO 3. In other words, the NMR behaviour of SPIRO 3 stands apart within the series and a reasonable explanation for it could be provided on the basis of its X-ray structure [3, 1-l]: in SPIRO 3, the four phosphorusnitrogen bonds associated with the P (loop) atom are practically equal, as well as the corresponding NPN endo- and exocyclic bond angles. Such a T,like environment for a phosphorus atom belonging to a kimeric ring is rather umque in cyclophosphazenes and may explain the peculiar NMR behaviour manifested by P (loop) in SPIRO 3. The X-ray structure of SPIRO 4 [4] indicates that the environment of P (loop) is as in other cyclophosbonds longer than PNendo bonds, NPN,,,, angles larger phazenes (PN,,, angles). Thus, we could expect the X-ray structures of than NPN,,, DISPIRO 3 and DISPIRO 4 to support this explanation of such structuredependent NMR behaviour. Unfortunately, single crystals of both chemicals are mined very rapidly under X-ray exposure_ We shall discuss this failure later. THE TRISF’IRO 3 DERIVATNE

Synthesis The synthesis of TRISPIRO 3 was carried out in the same mixture of solvents as for the DISPEL0 products. Three routes were followed: TABLE

1 Cbemcal

Compound

PCI, Sprro-N,P,Cle (SPIRO 3) Dsprro-N,P,Cl, (DISPIRO 3)

[HN--
2139 20 09

[I-TN-_(CH,),--rUi]

SpueN,P,Cl,[HN-_(CH*),(SPIRO 4) Dtsplr~N,P,Cl,[HN-_(CH,),--MI] (DISPIRO 4)

1

NH]

t

22 53 21.39 20 25 21.47 20 18 25 66 24 33 22 92

shift (solvent

pa00P)

CD&l,)

AG'Gl,)-Copm)

8 87 7 58 6.37 13 06 1191

13 16

14 36 13 07 11.78 17 19 15 90

(loo~)l

IJ

&I

_-pi Ref

4168

3

8 91

47 06

Ths

‘7 76

47 06

4

7 75

47 06

Thzs study

study

79

(1) The one-step route in which a mixture of N3P3C16 and of 1,3diaminopropane (l-6) is allowed to react at room temperatlxe for 4 h (Chivers’ technique [ 91); (2) the one-step route in which the DISPIRO 3 is allowed to react with a suitable excess of diamine; (3) the two-step route in which the MONOSPIRO 3 derivative is obtained and purified in the first step and then allowed to react with a suitable excess of diamine to lead to the expectid TRISPIRO chemical. In every case, “suitable excess” means that the diamme is not only used for grafting the SPIRO loops on the N3P3 nng but also for trapping HCl. It is noteworthy that the yield of all these reactions drops dramatically either (1) when any other HCl-trapping amine is used or (ii) as soon as the ratio for the mixture of solvents differs from the exact (7:3) value. Mass spec trome try The 70-eV electron-impact mass spectrum of TRISPIRO 3 (n/l = 351.28) IS shown in Fig. 4. The molecular ion M’ was observed as expected at m/z 351(68.6%) with satellites at m/z 350(8.9%) and 352(15-l%). There exists here a unique fragmentation route, firstly involvmg losses of lCH2, 2CH,, 3CHz, 3CH2 + 1NH and 3CHz + 2NH (associated with Htransfers) to give maximal peaks at m/z 337(0.3%), 321(4.6%), 309(3-l%), 295(20.5%) and 280(100.0%). Thus, the loss of one SPIRO loop leads to the base peak m/z 280 (correspondmg fragment coded as Ml). The two remaming loops in Ml are fragmented successively as above. the successive loss from Ml of 1CH2, 2CH1,, 3CHz, 3CH2 + 1NH and 3CHz f 2NH gives maximal peaks at m/z 266(1.9%), 251(7.7%), 237(2.7%)

r

50

90

Fig 4. Electron-Impact (70-eV)

570

410

kM

mass spectrum of TRISPIRO

3

80

223(10.4%) and 208(10.4%). Fragmentation of the last loop from the m/z 178(5.0%), 166(4.6%), 208 fragment gives peaks at m/z 194(3.1%), 149(14.3%) and 135(1.5%). Incidentally, the m/z 135 peak, corresponding to the N3PB ring fragment, is observed here in contrast with DISPIR.0 3 situation. In the low-mass range, peaks are observed (as in DISPIRO 3) at m/z and HN57(22,40/c) and 71(13.5%), w hich correspond to the HN-(CH2)3 (CH&-N fragments. X-ray

structure

of TRISPIRO

3

X-ray investigation of the TRISPIRO 3 structure displayed some interesting serendipitous features. TRISPIRO 3 crystallizes spontaneously at the end of the synthetic process, giving rise to single crystals suitable for X-ray analysis (solvent: ‘7:3 mixture of n-hexane and methylene chloride). However, such crystals are ruined very rapidly upon X-ray exposure and it was impossible to get enough reflections for structure refinement, even by using several crystals in sequence. A decrease of temperature from 300 K to 133 K did not help. In order to improve the quality and the size of single crystals, we recrystallized TRISPIRO 3 in many solvents and/or mixtures of solvents and large single crystals were obtained m this way from methanol. Such crystals, inserted ‘in a Lindemann capillary, were photographically investigated using a Weissenberg camera and Ni-filtered Cu Ko radiation; the space group obtained here appeared to differ from the one which had been determined for the previous single crystals. Thus, the following problem had to be solved: either the two kinds of single crystals belong to two allotropic varieties of TRISPIR.0 3 (hke SOAz [12] ) or crystals from methanol have clathrated some molecules of solvent (like MYKO 63 [13-161 or Allcock’s clathrate Cl71 1. One single crysral from methanol was transferred to a SYNTEX P21 computer-controlled diffractometer. Fifteen reflections were used to orientate the crystal and to refine the cell dimensions. Data could be collected straightforwardly. The structure was determined using direct methods included in the MULTAN SO program [18]. The refinement was performed taking into account anisotropic vibration for all atoms, except hydrogen. Fourier difference syntheses phased by the P, N and C atoms revealed not only the H atoms but also some extra electron densities located within intermolecular spaces which could be assigned to oxygen atoms of water (?) molecules clathrated to the TRISPIRO 3 molecules. Refinement of this clathrate was then achieved (final R = 0.094): the crystal structure is built from 4[TRISPIRO - 2Hz0] moieties, tnclinic system, space group Pi, cell parameters (I = 14.645(2), b = 11.518(4), c = 11.381(3) A, cy= 86.56(4), 0 = 103.58(2), .y = 103.92(4)“, V = 1811.27(5) A3. Thus, single crystals of TRISPIRO 3 are not broken down by X-ray beams

81

when water molecules are clathrated m the unit cell. These water molecules come from the wet commercial methanol which had been used for re-crystalhzation. Methanol itself does not clathrate TRISPIRO 3; no suitable single crystals have been obtained from solutions in dry methanol. Two crystallographically independent molecules, TRISPIRO 3A and TRISPIRO 3B, exist in the unit cell. Perspective views of these two forms (with the numbering of atoms) are represented in Figs. 5 and 6. The two molecular structures differ essentially in the conformation of one of the three loops, the two others being rather superimposable. It IS noteworthy that neither the 3A nor the 3B form admits any symmetry element, i.e., neither two-fold nor three-fold axis. In other words, the three SPIRO loops in both 3A and 3B are not arranged in the “propeller-IIke” pattern which would have been expected if a three-fold axis had existed m the molecules. Main bond lengths and bond angles for 3A and 3B are listed in Table 2. Fractional atomic coordinates are given in Table 3.

Fig. 5 Perspective

mew of the TRISPIRO

3A form.

82

Fig. 6. Perspective

view of the TRISPIRO

3B form.

The perspective view of the unit cell (the 3A and 3B forms being drawn with white and black bonds for the N3P3 ring, respectively), as shown in Fig. 7, explains the remarkable stability of the crystal when irradiated. Two striking features are conspicuous: (i) the stacking in the crystal is due to strong intermolecular hydrogen bonds between oxygen atoms and suitable couples of NEIgroups of the loops (04-N7: 3.79 A; 04-N8: 3.16 8,; 02N13i: 3.65 A; 02-N14i: 3.96 A; Ol-N8: 3.80 A and 03-N14i: 3.44 a);

(ii) even more interesting is the manner in which the eight oxygen atoms are arranged in the unit cell: they form a kind of water-course (indicated by dotted lines in Fig. 7) running between laminae of cyclophosphazenes, distances such as 01-03, 03-04 and 04-02 being about 2.80 A9 that is comparable to the 2.75 A value in ice. Thus, the two kinds of hydrogen bonds which exist in the unit cell confer a remarkable stability to the crystal, roughly similar to that in a crystal of ice. This is the explanation of the fact that crystals of this TRISPIRO dihydrate are so stable upon X-ray irradiation.

83

TABLE Main

2

bond

lengths

(A)

and bond

angles (“) m the TRISPIRO

TRISPIRO

3B

TRISPIRO

P4-N4 P4-N6 P5-N5 P5-N6 P6-N4 P6-N5 P4-N13 P4-N14 P&N15 P5-N16 %-N17 P6-N18 N13-ClO N14-Cl2 ClO-Cll Cll-Cl2 N15-Cl3 N16-Cl5 C13-cl4 C14-Cl5 N17-Cl6 NlS-Cl7 Cl6- Cl8 C18-Cl7

1602(5) 1610(6) 1592(5) 1600(4) 1599(3) 1611(6) 1658<6) 1647(5) 1.666(4) 1664(4) 1655(5) 1.652(4) 1454(15) 1460(14) 1486(17) 1485(21) 1462(11) 1.488<11) 1544(13) 1442(17) 1464(11) 1;40<12) 1490(15) 1486(20)

Pl-Nl-P3 Pl-N3-P2 P2-N2-P3 Nl-Pl-N3 Nl-P3-N2 N2-P2-N3 N7-Pl-N9 N9-P2-NlO Nll-P3-N12

Bondlengths TRISPIRO

TABLE

1.598(4) 1.594<3) 1.596(5) 1.602<7) 1593(5) 1605(7) 1.673(5) 1661(4) l-654(5) 1.655(4) 1.640<3) 1650(5) 1446(12) 1452(12) 1525(16) 1493(13) 1464<10) 1.474(13) 1.493(16) 1.521(15) 1.448(14) 1428(19) 1.453(18) 1.467(18)

Pl P2 P3 Nl N2 N3 N7 N8 N9 NlO Nil N12 01 02

03

04 05 06 07 08 09

34

TRISPIRO

123 6(2) 1233<2) 120 5(4) 114 5(3) 115 3(4) 1150(3) 99 3(2) 1040(3) 1033(4)

3B

P4-N4-P6 123 S(4) P4-N6P5 1211<3) P5-N5-P6 1220(4) N4-P4-N6 114 8(4) N5-P+N6 116 9(3) N4-P6N5 114 5(4) N13-P4-N141026(3) N15-P5-N16 1015(3) N17-P6-N18 1004<5)

3

Fractional atomic 3B and oxygens AtollI

3B forms

Bondanglese)

3A

Pl-Nl Pl-N3 P2-N2 P2-N3 P3-Nl P3-N2 Pl-N7 Pl-N8 P2-N9 P2-NlO P3-Nll P3-N12 N7-Cl N8-C3 Cl42 C2-C3 NS-C6 NlO-C4 c-5 C&C6 Nll-C7 N12-C8 CS-CS c&c9

3A and TRISPIRO

coordmates

x/a

0.1929(l) 0.0682(l) 0.0729(l) O-1464(5) 0.0194(5) 0.1398(5) 0.3116(5) 0.1950(5) -0.0199(5) 0.1247(5) 0.1296(5) -0.0097(5) 0.3759(7) 0.3654<7) 0.2634(7) 0.1378(9) 0.0460(10) -0.0056(7) 00735(7) 0.0089(8) -0.0535(11)

with

Y/b

0.0518(2) -O-0796(2) 0.1618(2) O-1614(6) 0.0315(6) -0.0707(6) 0.0925(7) 00379(7) -0.2009<6) -0.0941<6) 0.2437<6) 0.2337<7) 0.0274(9) 0.0273(9) -00217(9) +X2150(10) -0.3089<9) -0.3169(g) 0.2918(9) 03578(10) 0.296705)

e s.d.‘s

z/c

In parentheses

AtOm

0 5742(2) P4 0.7147(2) P5 O-6674(2) P6 05842(7) N4 0.7080<6) N5 0.6260(6) N6 06327(6) N13 04312(6) N14 0.6893<6) Nl5 0.8564(6) N16 0.7872(7) N17 05988<6) N18 0.6033(g) 010 04668(10)011 0.4016(9) 012 08954(g) 013 0 8712<10)014 0.7382<10)015 0 8527t9) 016 0.7753(11)017 06658(13)018 01 02 03 04

for TRISPIRO

3A, TRISPIRO

z/c

x/a

r/b

0 5423(l) 04024(l) 03675(l) 0 3425(5) 0.4762(5) 0 5098(5) 0.5475(5) 06546(5) 0.4038(5) 03363(5) 03484(5) 0 2853(5) 06323(g) 0.7365(S) 0.7252(9) 0.4314(S) 03662(g) 03694<7) 03257(8) 0.2442(9) 0.2598(9)

0 2832<2) 0 4724(2) 03811(6) 04897(6) 0.3089(6) 03216(7) 04732(7) 0 2617(6) 0.1508(7) 06024(S) 0.4352(7) 0 2739(S) 0.4236(11) 03646(14) 01526(g) 0.0400(9) 0.0464(g) 0.6853(g) 06276<11) 05185(11)

0.8255(2) 0.9514(2) 07956(2) 0 9017<6) 0.7784(6) 0.9308(6) 0.7089<6) 08717(6) 1.0972(6) 0 8925(6) 0.8229(6) 0 6699(6) 07163(11) 08672(12) 0.7501(13) 1.1510<9) 1.0819<11) 09561(11) 0.7234(S) 0.6247(12) 05760(g)

00835(6) 0.4693(6) 0 2047(6) 0.2646(6)

00098(7) 03890(8) 0 2412(9) 0 3141(7)

0.0939<7) 04341(7) 0.1394c8) 0 3800(S)

0

3969(2)

84

Fig. 7. Perspective view of the unit cell showing the “water-course” and the pattern of hydrcgen bonds.

of water molecules

We tried to make use of this “dihydrate-tick” Zor reaching molecular structures of DISPIRO 3 and DISPIRO 4. Unfortunately, we have failed so far in obtaining suitable single crystals of such DISPIRO dihydrate from solutions in wet methanol: in every case, single crystals of the genuine chemicals are obtained which break down under X-ray exposure. The fact that DISPIRO compounds are not able to take up water from wet methanol may be related to the lower acidic character of Ns_ hydrogens, as measured

by IR spectroscopy [ 191.

CONCLUSIONS

The reaction of N3P3C16 with 1,3-diaminopropane and 1,4diaminobutane in suitable non polar solvents allows the synthesis in a very high yield of the PNIJR-containing DISPIRO and TRISPIRO derivatives without any significant side-polymerization. Single crystals of all chemicals may be obtained very easily at the end of the synthetic process but they are ruined upon X-ray exposure, preventing elucidation of molecular structures. We could, however, approach the molecular structure of TRISPIRO 3 through an X-ray investigation of its dihydrate as obtained from solutions in wet methanol. The versatility of the SPIRO loop conformation within SPIRO-, DISPIRO- and TRISPIRO-cyclotriphosphazenes is now under investigation in this laboratory by using suitable quantum techniques [20].

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