Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101015359/gg1084sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101015359/gg1084IIsup2.hkl |
CCDC reference: 179269
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).
H atoms were placed geometrically and refined using a riding model with the SHELXL97 (Sheldrick, 1997) defaults.
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.
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. |
C5H10Cl4N3O2P3 | F(000) = 760 |
Mr = 378.87 | Dx = 1.714 Mg m−3 |
Monoclinic, P21/n | Melting point: 427-428K K |
Hall symbol: -p_2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 12.106 (2) Å | Cell parameters from 25 reflections |
b = 7.708 (2) Å | θ = 9.5–12.0° |
c = 15.776 (2) Å | µ = 1.13 mm−1 |
β = 93.997 (10)° | T = 293 K |
V = 1468.5 (5) Å3 | Rectangular block, colourless |
Z = 4 | 0.4 × 0.3 × 0.2 mm |
Enraf-Nonius MACH3 diffractometer | 2135 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.014 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
profile data from ω scans | h = 0→14 |
Absorption correction: ψ-scan (DATCOR; Reibenspies, 1989) | k = 0→9 |
Tmin = 0.662, Tmax = 0.806 | l = −18→18 |
2693 measured reflections | 3 standard reflections every 90 min |
2571 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-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 reflections | Δρmax = 0.29 e Å−3 |
157 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0198 (11) |
C5H10Cl4N3O2P3 | V = 1468.5 (5) Å3 |
Mr = 378.87 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.106 (2) Å | µ = 1.13 mm−1 |
b = 7.708 (2) Å | T = 293 K |
c = 15.776 (2) Å | 0.4 × 0.3 × 0.2 mm |
β = 93.997 (10)° |
Enraf-Nonius MACH3 diffractometer | 2135 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (DATCOR; Reibenspies, 1989) | Rint = 0.014 |
Tmin = 0.662, Tmax = 0.806 | 3 standard reflections every 90 min |
2693 measured reflections | intensity decay: none |
2571 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.29 e Å−3 |
2571 reflections | Δρmin = −0.28 e Å−3 |
157 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.79618 (5) | 0.16178 (8) | 0.55887 (4) | 0.03942 (18) | |
P2 | 0.68778 (5) | 0.13328 (7) | 0.39980 (4) | 0.03753 (17) | |
P3 | 0.74190 (6) | 0.45278 (8) | 0.46501 (4) | 0.04539 (19) | |
Cl1 | 0.52712 (5) | 0.06854 (9) | 0.39184 (5) | 0.0573 (2) | |
Cl2 | 0.73638 (6) | 0.01798 (11) | 0.29600 (4) | 0.0622 (2) | |
Cl3 | 0.86624 (7) | 0.59767 (11) | 0.42789 (5) | 0.0714 (2) | |
Cl4 | 0.62883 (7) | 0.63274 (10) | 0.48496 (6) | 0.0769 (3) | |
O1 | 0.74559 (13) | 0.0968 (2) | 0.64185 (11) | 0.0492 (4) | |
O2 | 0.92300 (13) | 0.1267 (2) | 0.57436 (10) | 0.0475 (4) | |
N1 | 0.74802 (19) | 0.0486 (3) | 0.48000 (13) | 0.0511 (6) | |
N2 | 0.6983 (2) | 0.3359 (3) | 0.38729 (13) | 0.0527 (6) | |
N3 | 0.7768 (2) | 0.3643 (3) | 0.55212 (14) | 0.0570 (6) | |
C1 | 0.7805 (2) | −0.0748 (4) | 0.67355 (17) | 0.0507 (6) | |
H1A | 0.7556 | −0.1625 | 0.6324 | 0.061* | |
H1B | 0.7462 | −0.0986 | 0.7261 | 0.061* | |
C2 | 0.9052 (2) | −0.0853 (4) | 0.68916 (15) | 0.0469 (6) | |
C3 | 0.9570 (2) | −0.0442 (4) | 0.60650 (16) | 0.0487 (6) | |
H3A | 1.0370 | −0.0477 | 0.6158 | 0.058* | |
H3B | 0.9349 | −0.1316 | 0.5645 | 0.058* | |
C21 | 0.9358 (3) | −0.2740 (5) | 0.7121 (2) | 0.0852 (11) | |
H21A | 0.9031 | −0.3057 | 0.7637 | 0.128* | |
H21B | 1.0148 | −0.2846 | 0.7201 | 0.128* | |
H21C | 0.9085 | −0.3495 | 0.6670 | 0.128* | |
C22 | 0.9459 (3) | 0.0399 (6) | 0.75896 (18) | 0.0792 (11) | |
H22A | 0.9297 | 0.1567 | 0.7411 | 0.119* | |
H22B | 1.0244 | 0.0266 | 0.7702 | 0.119* | |
H22C | 0.9093 | 0.0153 | 0.8097 | 0.119* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0459 (3) | 0.0396 (3) | 0.0316 (3) | −0.0032 (3) | −0.0051 (2) | 0.0009 (2) |
P2 | 0.0441 (3) | 0.0323 (3) | 0.0347 (3) | −0.0015 (2) | −0.0077 (2) | −0.0027 (2) |
P3 | 0.0581 (4) | 0.0301 (3) | 0.0465 (4) | −0.0052 (3) | −0.0063 (3) | −0.0007 (3) |
Cl1 | 0.0431 (3) | 0.0604 (4) | 0.0675 (4) | −0.0038 (3) | −0.0018 (3) | −0.0015 (3) |
Cl2 | 0.0612 (4) | 0.0769 (5) | 0.0482 (4) | 0.0046 (4) | 0.0008 (3) | −0.0202 (3) |
Cl3 | 0.0746 (5) | 0.0652 (5) | 0.0741 (5) | −0.0272 (4) | 0.0028 (4) | −0.0003 (4) |
Cl4 | 0.0763 (5) | 0.0458 (4) | 0.1080 (7) | 0.0106 (4) | 0.0023 (5) | −0.0067 (4) |
O1 | 0.0418 (9) | 0.0616 (11) | 0.0445 (9) | 0.0093 (8) | 0.0049 (7) | 0.0103 (8) |
O2 | 0.0439 (9) | 0.0594 (11) | 0.0391 (9) | −0.0084 (8) | 0.0014 (7) | 0.0092 (8) |
N1 | 0.0729 (15) | 0.0315 (10) | 0.0454 (12) | −0.0003 (10) | −0.0206 (11) | 0.0010 (9) |
N2 | 0.0752 (15) | 0.0357 (11) | 0.0442 (11) | −0.0087 (10) | −0.0173 (10) | 0.0061 (9) |
N3 | 0.0878 (17) | 0.0393 (12) | 0.0414 (11) | −0.0024 (11) | −0.0130 (11) | −0.0071 (9) |
C1 | 0.0458 (14) | 0.0583 (16) | 0.0484 (14) | 0.0012 (12) | 0.0073 (11) | 0.0165 (12) |
C2 | 0.0437 (13) | 0.0618 (16) | 0.0349 (12) | 0.0065 (12) | 0.0008 (10) | 0.0092 (11) |
C3 | 0.0389 (12) | 0.0640 (17) | 0.0432 (13) | 0.0060 (12) | 0.0031 (10) | 0.0035 (12) |
C21 | 0.080 (2) | 0.089 (3) | 0.088 (2) | 0.030 (2) | 0.0160 (19) | 0.042 (2) |
C22 | 0.070 (2) | 0.128 (3) | 0.0375 (15) | 0.007 (2) | −0.0124 (13) | −0.0102 (17) |
P1—N1 | 1.596 (2) | C1—C2 | 1.515 (3) |
P1—N3 | 1.581 (2) | C1—H1A | 0.9700 |
P1—O1 | 1.5656 (18) | C1—H1B | 0.9700 |
P1—O2 | 1.5613 (18) | C2—C21 | 1.538 (4) |
P2—Cl1 | 2.0034 (9) | C2—C22 | 1.520 (4) |
P2—Cl2 | 1.9880 (9) | C2—C3 | 1.519 (3) |
P2—N1 | 1.559 (2) | C3—H3A | 0.9700 |
P2—N2 | 1.581 (2) | C3—H3B | 0.9700 |
P3—Cl3 | 1.9946 (10) | C21—H21A | 0.9600 |
P3—Cl4 | 1.9892 (11) | C21—H21B | 0.9600 |
P3—N2 | 1.582 (2) | C21—H21C | 0.9600 |
P3—N3 | 1.565 (2) | C22—H22A | 0.9600 |
O1—C1 | 1.466 (3) | C22—H22B | 0.9600 |
O2—C3 | 1.461 (3) | C22—H22C | 0.9600 |
N1—P1—N3 | 116.26 (11) | C2—C1—H1B | 109.4 |
O1—P1—O2 | 104.57 (9) | H1A—C1—H1B | 108.0 |
O1—P1—N1 | 109.52 (11) | C1—C2—C3 | 108.4 (2) |
O1—P1—N3 | 107.88 (12) | C1—C2—C22 | 110.7 (2) |
O2—P1—N1 | 109.22 (11) | C3—C2—C22 | 110.9 (2) |
O2—P1—N3 | 108.75 (12) | C1—C2—C21 | 108.0 (2) |
Cl1—P2—Cl2 | 100.29 (4) | C3—C2—C21 | 107.0 (2) |
N1—P2—Cl1 | 110.11 (9) | C22—C2—C21 | 111.6 (3) |
N1—P2—Cl2 | 109.45 (9) | O2—C3—C2 | 111.3 (2) |
N1—P2—N2 | 118.54 (11) | O2—C3—H3A | 109.4 |
N2—P2—Cl1 | 108.95 (9) | C2—C3—H3A | 109.4 |
N2—P2—Cl2 | 107.93 (9) | O2—C3—H3B | 109.4 |
Cl3—P3—Cl4 | 101.40 (5) | C2—C3—H3B | 109.4 |
N2—P3—Cl3 | 107.99 (10) | H3A—C3—H3B | 108.0 |
N2—P3—Cl4 | 108.88 (10) | C2—C21—H21A | 109.5 |
N3—P3—Cl3 | 109.81 (10) | C2—C21—H21B | 109.5 |
N3—P3—Cl4 | 108.14 (10) | H21A—C21—H21B | 109.5 |
N2—P3—N3 | 119.16 (11) | C2—C21—H21C | 109.5 |
P1—N1—P2 | 121.92 (13) | H21A—C21—H21C | 109.5 |
P1—N3—P3 | 121.27 (13) | H21B—C21—H21C | 109.5 |
P2—N2—P3 | 119.42 (13) | C2—C22—H22A | 109.5 |
C1—O1—P1 | 116.97 (15) | C2—C22—H22B | 109.5 |
C3—O2—P1 | 117.42 (15) | H22A—C22—H22B | 109.5 |
O1—C1—C2 | 111.3 (2) | C2—C22—H22C | 109.5 |
O1—C1—H1A | 109.4 | H22A—C22—H22C | 109.5 |
C2—C1—H1A | 109.4 | H22B—C22—H22C | 109.5 |
O1—C1—H1B | 109.4 |
Experimental details
Crystal data | |
Chemical formula | C5H10Cl4N3O2P3 |
Mr | 378.87 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 12.106 (2), 7.708 (2), 15.776 (2) |
β (°) | 93.997 (10) |
V (Å3) | 1468.5 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Enraf-Nonius MACH3 diffractometer |
Absorption correction | ψ-scan (DATCOR; Reibenspies, 1989) |
Tmin, Tmax | 0.662, 0.806 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2693, 2571, 2135 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.083, 1.07 |
No. of reflections | 2571 |
No. of parameters | 157 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
P1—N1 | 1.596 (2) | P2—N1 | 1.559 (2) |
P1—N3 | 1.581 (2) | P2—N2 | 1.581 (2) |
P1—O1 | 1.5656 (18) | P3—Cl3 | 1.9946 (10) |
P1—O2 | 1.5613 (18) | P3—Cl4 | 1.9892 (11) |
P2—Cl1 | 2.0034 (9) | P3—N2 | 1.582 (2) |
P2—Cl2 | 1.9880 (9) | P3—N3 | 1.565 (2) |
N1—P1—N3 | 116.26 (11) | Cl3—P3—Cl4 | 101.40 (5) |
O1—P1—O2 | 104.57 (9) | N2—P3—Cl3 | 107.99 (10) |
O1—P1—N1 | 109.52 (11) | N2—P3—Cl4 | 108.88 (10) |
O1—P1—N3 | 107.88 (12) | N3—P3—Cl3 | 109.81 (10) |
O2—P1—N1 | 109.22 (11) | N3—P3—Cl4 | 108.14 (10) |
O2—P1—N3 | 108.75 (12) | N2—P3—N3 | 119.16 (11) |
Cl1—P2—Cl2 | 100.29 (4) | P1—N1—P2 | 121.92 (13) |
N1—P2—Cl1 | 110.11 (9) | P1—N3—P3 | 121.27 (13) |
N1—P2—Cl2 | 109.45 (9) | P2—N2—P3 | 119.42 (13) |
N1—P2—N2 | 118.54 (11) | C1—O1—P1 | 116.97 (15) |
N2—P2—Cl1 | 108.95 (9) | C3—O2—P1 | 117.42 (15) |
N2—P2—Cl2 | 107.93 (9) |
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.