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The title spiro­cyclic compound (alternative name: 2,2,4,4-tetra­chloro-9,9-di­methyl-7,11-dioxa-1,3,5-tri­aza-2λ5,4λ5,6λ5-triphospha­spiro­[5.5]­undeca-1,3,5-triene), C5H10Cl4N3O2P3, does not contain alternating long–short P—N bond lengths in the phosphazene ring [P—N 1.559 (2)–1.596 (2) Å], as are observed in other analogous spiro­cyclic compounds. The six-membered phosphazene ring has a chair conformation in the solid state, but a conformational equilibrium in solution is indicated by NMR spectroscopy.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101015359/gg1084sup1.cif
Contains datablocks global, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101015359/gg1084IIsup2.hkl
Contains datablock II

CCDC reference: 179269

Comment top

We are interested in utilizing substituted cyclotriphosphazenes as bases in our synthetic research. Since the most readily accessible among these, N3P3Cl6, (I), has six reactive Cl atoms that can affect its utility, we wished to reduce the number of functionalities. One of the easiest ways to do this is to treat (I) with a suitable difunctional reagent and obtain `spiro' or `ansa' types of products (Contractor et al., 1984; Kumaraswamy et al., 1999; Chandrasekhar & Thomas, 1993). Since tetracoordinate PV compounds with six-membered rings at the P are more stable to hydrolysis than those with five-membered rings, the diol 2,2-dimethyl-1,3-propanediol, which is cheaper than 1,3-propanediol, was used as the starting material. Differences in the reactivity patterns of these two diols were also studied, as observed in the reaction of the cyclodiphosphazane, (III), [ClPN-tBu]2 (Kumaravel et al., 1987; Kommana & Kumara Swamy, 2000). We found that the reaction of (I) with 2,2-dimethyl-1,3-propanediol gave the title spirocyclic compound, (II), as the only product. Herein we report the X-ray structure of (II). \sch

An ORTEX drawing of (II) is shown in Fig. 1. The bond distances and angles are in the normal range expected for compounds of this type (Chandrasekhar & Thomas, 1993). The P1—N1 distance is the longest, but P1—N3 is close in length to N2—P3 and N2—P2. This pattern is slightly different from those observed in analogous monospirocyclic cyclotriphosphazenes (Contractor et al., 1985; Kumaraswamy et al., 1999), wherein a long-short-long pattern for the ring P—N bond lengths was noted. The P—Cl bond lengths are within the normal range observed for analogous compounds (Contractor et al., 1984; Kumaraswamy et al., 1999).

The phosphazene ring can be considered to be planar, the maximum deviation from planarity of 0.135 Å being observed for N3. The 1,3,2-dioxaphosphorinane ring has the usual chair form, with atoms C2 and P1 above and below the mean plane containing O1, O3, C1 and C3. Since this feature would make the two methyl groups and the two H atoms of each OCH2 group inequivalent (for examples giving NMR in solution and solid-state X-ray structures see Muthiah et al., 2000), the observed 1H NMR spectrum in solution (i.e. equivalence of the methyl and OCH2 H atoms) suggests a conformational equilibrium in solution.

Regarding intermolecular contacts, we note that atom C3 is close to O3 of a related molecule [C3···O3i 3.352 (3) Å; symmetry code: 2 - x, -y, 1 - z] and vice versa. The corresponding H3B···O3 distance is 2.88 Å. Although this is a minor point, it could be important in connection with our understanding of crystal packing and it has not been considered in the cyclophosphazene structures reported to date.

Related literature top

For related literature, see: Chandrasekhar & Thomas (1993); Contractor et al. (1984, 1985); Kommana & Kumara Swamy (2000); Kumaraswamy et al. (1999); Kumaravel et al. (1987); Muthiah et al. (2000); Sheldrick (1997).

Experimental top

To a solution of N3P3Cl6 (3.48 g, 10 mmol) in toluene (10 ml) was added a solution of 2,2-dimethyl-1,3-propanediol (1.04 g, 10 mmol) and triethylamine (2.02 g, 20 mmol) in toluene (10 ml) dropwise over 10 min with continuous stirring. The reaction mixture was then heated under reflux for 8 h, followed by filtration and removal of the solvent. The solid obtained was crystallized from dichloromethane-hexane (1:4) (yield 3.23 g, 85%; m.p. 427–428 K). Crystals were used for X-ray examination as obtained. 1H NMR (CDCl3, δ, p.p.m.): 1.10 [s, 6H, C(CH3)2], 4.12 (d, 3JP—H = 14.0 Hz, 4H, OCH2); 31P NMR: 1.3 (t, 2JPP = 69.6 Hz, Pspiro), 22.6 (d, 2JPP = 69.6 Hz, PCl2).

Refinement top

H atoms were placed geometrically and refined using a riding model with the SHELXL97 (Sheldrick, 1997) defaults.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: SDP (Frenz, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (II) showing the atom-numbering scheme. Displacement ellipsoids are shown at the 25% probability level and H atoms have been omitted for clarity.
4,4,6,6-Tetrachloro-2,2-(2,2-dimethylpropane-1,3-diyldioxy)- 1,3,5,2λ5,4λ5,6λ5-triazatriphosphorine top
Crystal data top
C5H10Cl4N3O2P3F(000) = 760
Mr = 378.87Dx = 1.714 Mg m3
Monoclinic, P21/nMelting point: 427-428K K
Hall symbol: -p_2ynMo Kα radiation, λ = 0.71073 Å
a = 12.106 (2) ÅCell parameters from 25 reflections
b = 7.708 (2) Åθ = 9.5–12.0°
c = 15.776 (2) ŵ = 1.13 mm1
β = 93.997 (10)°T = 293 K
V = 1468.5 (5) Å3Rectangular block, colourless
Z = 40.4 × 0.3 × 0.2 mm
Data collection top
Enraf-Nonius MACH3
diffractometer
2135 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
Graphite monochromatorθmax = 25.0°, θmin = 2.1°
profile data from ω scansh = 014
Absorption correction: ψ-scan
(DATCOR; Reibenspies, 1989)
k = 09
Tmin = 0.662, Tmax = 0.806l = 1818
2693 measured reflections3 standard reflections every 90 min
2571 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.083 w = 1/[σ2(Fo2) + (0.046P)2 + 0.6318P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2571 reflectionsΔρmax = 0.29 e Å3
157 parametersΔρmin = 0.28 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0198 (11)
Crystal data top
C5H10Cl4N3O2P3V = 1468.5 (5) Å3
Mr = 378.87Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.106 (2) ŵ = 1.13 mm1
b = 7.708 (2) ÅT = 293 K
c = 15.776 (2) Å0.4 × 0.3 × 0.2 mm
β = 93.997 (10)°
Data collection top
Enraf-Nonius MACH3
diffractometer
2135 reflections with I > 2σ(I)
Absorption correction: ψ-scan
(DATCOR; Reibenspies, 1989)
Rint = 0.014
Tmin = 0.662, Tmax = 0.8063 standard reflections every 90 min
2693 measured reflections intensity decay: none
2571 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.07Δρmax = 0.29 e Å3
2571 reflectionsΔρmin = 0.28 e Å3
157 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.79618 (5)0.16178 (8)0.55887 (4)0.03942 (18)
P20.68778 (5)0.13328 (7)0.39980 (4)0.03753 (17)
P30.74190 (6)0.45278 (8)0.46501 (4)0.04539 (19)
Cl10.52712 (5)0.06854 (9)0.39184 (5)0.0573 (2)
Cl20.73638 (6)0.01798 (11)0.29600 (4)0.0622 (2)
Cl30.86624 (7)0.59767 (11)0.42789 (5)0.0714 (2)
Cl40.62883 (7)0.63274 (10)0.48496 (6)0.0769 (3)
O10.74559 (13)0.0968 (2)0.64185 (11)0.0492 (4)
O20.92300 (13)0.1267 (2)0.57436 (10)0.0475 (4)
N10.74802 (19)0.0486 (3)0.48000 (13)0.0511 (6)
N20.6983 (2)0.3359 (3)0.38729 (13)0.0527 (6)
N30.7768 (2)0.3643 (3)0.55212 (14)0.0570 (6)
C10.7805 (2)0.0748 (4)0.67355 (17)0.0507 (6)
H1A0.75560.16250.63240.061*
H1B0.74620.09860.72610.061*
C20.9052 (2)0.0853 (4)0.68916 (15)0.0469 (6)
C30.9570 (2)0.0442 (4)0.60650 (16)0.0487 (6)
H3A1.03700.04770.61580.058*
H3B0.93490.13160.56450.058*
C210.9358 (3)0.2740 (5)0.7121 (2)0.0852 (11)
H21A0.90310.30570.76370.128*
H21B1.01480.28460.72010.128*
H21C0.90850.34950.66700.128*
C220.9459 (3)0.0399 (6)0.75896 (18)0.0792 (11)
H22A0.92970.15670.74110.119*
H22B1.02440.02660.77020.119*
H22C0.90930.01530.80970.119*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0459 (3)0.0396 (3)0.0316 (3)0.0032 (3)0.0051 (2)0.0009 (2)
P20.0441 (3)0.0323 (3)0.0347 (3)0.0015 (2)0.0077 (2)0.0027 (2)
P30.0581 (4)0.0301 (3)0.0465 (4)0.0052 (3)0.0063 (3)0.0007 (3)
Cl10.0431 (3)0.0604 (4)0.0675 (4)0.0038 (3)0.0018 (3)0.0015 (3)
Cl20.0612 (4)0.0769 (5)0.0482 (4)0.0046 (4)0.0008 (3)0.0202 (3)
Cl30.0746 (5)0.0652 (5)0.0741 (5)0.0272 (4)0.0028 (4)0.0003 (4)
Cl40.0763 (5)0.0458 (4)0.1080 (7)0.0106 (4)0.0023 (5)0.0067 (4)
O10.0418 (9)0.0616 (11)0.0445 (9)0.0093 (8)0.0049 (7)0.0103 (8)
O20.0439 (9)0.0594 (11)0.0391 (9)0.0084 (8)0.0014 (7)0.0092 (8)
N10.0729 (15)0.0315 (10)0.0454 (12)0.0003 (10)0.0206 (11)0.0010 (9)
N20.0752 (15)0.0357 (11)0.0442 (11)0.0087 (10)0.0173 (10)0.0061 (9)
N30.0878 (17)0.0393 (12)0.0414 (11)0.0024 (11)0.0130 (11)0.0071 (9)
C10.0458 (14)0.0583 (16)0.0484 (14)0.0012 (12)0.0073 (11)0.0165 (12)
C20.0437 (13)0.0618 (16)0.0349 (12)0.0065 (12)0.0008 (10)0.0092 (11)
C30.0389 (12)0.0640 (17)0.0432 (13)0.0060 (12)0.0031 (10)0.0035 (12)
C210.080 (2)0.089 (3)0.088 (2)0.030 (2)0.0160 (19)0.042 (2)
C220.070 (2)0.128 (3)0.0375 (15)0.007 (2)0.0124 (13)0.0102 (17)
Geometric parameters (Å, º) top
P1—N11.596 (2)C1—C21.515 (3)
P1—N31.581 (2)C1—H1A0.9700
P1—O11.5656 (18)C1—H1B0.9700
P1—O21.5613 (18)C2—C211.538 (4)
P2—Cl12.0034 (9)C2—C221.520 (4)
P2—Cl21.9880 (9)C2—C31.519 (3)
P2—N11.559 (2)C3—H3A0.9700
P2—N21.581 (2)C3—H3B0.9700
P3—Cl31.9946 (10)C21—H21A0.9600
P3—Cl41.9892 (11)C21—H21B0.9600
P3—N21.582 (2)C21—H21C0.9600
P3—N31.565 (2)C22—H22A0.9600
O1—C11.466 (3)C22—H22B0.9600
O2—C31.461 (3)C22—H22C0.9600
N1—P1—N3116.26 (11)C2—C1—H1B109.4
O1—P1—O2104.57 (9)H1A—C1—H1B108.0
O1—P1—N1109.52 (11)C1—C2—C3108.4 (2)
O1—P1—N3107.88 (12)C1—C2—C22110.7 (2)
O2—P1—N1109.22 (11)C3—C2—C22110.9 (2)
O2—P1—N3108.75 (12)C1—C2—C21108.0 (2)
Cl1—P2—Cl2100.29 (4)C3—C2—C21107.0 (2)
N1—P2—Cl1110.11 (9)C22—C2—C21111.6 (3)
N1—P2—Cl2109.45 (9)O2—C3—C2111.3 (2)
N1—P2—N2118.54 (11)O2—C3—H3A109.4
N2—P2—Cl1108.95 (9)C2—C3—H3A109.4
N2—P2—Cl2107.93 (9)O2—C3—H3B109.4
Cl3—P3—Cl4101.40 (5)C2—C3—H3B109.4
N2—P3—Cl3107.99 (10)H3A—C3—H3B108.0
N2—P3—Cl4108.88 (10)C2—C21—H21A109.5
N3—P3—Cl3109.81 (10)C2—C21—H21B109.5
N3—P3—Cl4108.14 (10)H21A—C21—H21B109.5
N2—P3—N3119.16 (11)C2—C21—H21C109.5
P1—N1—P2121.92 (13)H21A—C21—H21C109.5
P1—N3—P3121.27 (13)H21B—C21—H21C109.5
P2—N2—P3119.42 (13)C2—C22—H22A109.5
C1—O1—P1116.97 (15)C2—C22—H22B109.5
C3—O2—P1117.42 (15)H22A—C22—H22B109.5
O1—C1—C2111.3 (2)C2—C22—H22C109.5
O1—C1—H1A109.4H22A—C22—H22C109.5
C2—C1—H1A109.4H22B—C22—H22C109.5
O1—C1—H1B109.4

Experimental details

Crystal data
Chemical formulaC5H10Cl4N3O2P3
Mr378.87
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)12.106 (2), 7.708 (2), 15.776 (2)
β (°) 93.997 (10)
V3)1468.5 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.13
Crystal size (mm)0.4 × 0.3 × 0.2
Data collection
DiffractometerEnraf-Nonius MACH3
diffractometer
Absorption correctionψ-scan
(DATCOR; Reibenspies, 1989)
Tmin, Tmax0.662, 0.806
No. of measured, independent and
observed [I > 2σ(I)] reflections
2693, 2571, 2135
Rint0.014
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.083, 1.07
No. of reflections2571
No. of parameters157
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.28

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SDP (Frenz, 1985), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), SHELXL97.

Selected geometric parameters (Å, º) top
P1—N11.596 (2)P2—N11.559 (2)
P1—N31.581 (2)P2—N21.581 (2)
P1—O11.5656 (18)P3—Cl31.9946 (10)
P1—O21.5613 (18)P3—Cl41.9892 (11)
P2—Cl12.0034 (9)P3—N21.582 (2)
P2—Cl21.9880 (9)P3—N31.565 (2)
N1—P1—N3116.26 (11)Cl3—P3—Cl4101.40 (5)
O1—P1—O2104.57 (9)N2—P3—Cl3107.99 (10)
O1—P1—N1109.52 (11)N2—P3—Cl4108.88 (10)
O1—P1—N3107.88 (12)N3—P3—Cl3109.81 (10)
O2—P1—N1109.22 (11)N3—P3—Cl4108.14 (10)
O2—P1—N3108.75 (12)N2—P3—N3119.16 (11)
Cl1—P2—Cl2100.29 (4)P1—N1—P2121.92 (13)
N1—P2—Cl1110.11 (9)P1—N3—P3121.27 (13)
N1—P2—Cl2109.45 (9)P2—N2—P3119.42 (13)
N1—P2—N2118.54 (11)C1—O1—P1116.97 (15)
N2—P2—Cl1108.95 (9)C3—O2—P1117.42 (15)
N2—P2—Cl2107.93 (9)
 

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