2,4-Bis[bis(diisopropyl­amino)­phos­phanyl]-1,2,3,4-tetra­phospha­bicyclo[1.1.0]butane

Agnieszka Łapczuk-Krygier; Katarzyna Baranowska; Jerzy Pikies

doi:10.1107/S1600536808037938

. 2008 Nov 22;64(Pt 12):o2427. doi: 10.1107/S1600536808037938

2,4-Bis[bis(diisopropylamino)phosphanyl]-1,2,3,4-tetraphosphabicyclo[1.1.0]butane

Agnieszka Łapczuk-Krygier ^a, Katarzyna Baranowska ^a,^*, Jerzy Pikies ^a

PMCID: PMC2959955 PMID: 21581395

Abstract

The title compound, C₂₄H₅₆N₄P₆ or (ⁱPr₂N)₂P–P₄–P(NⁱPr₂)₂, adopts a butterfly structure, with planar environments for the N atoms and pyramidal environments for the P atoms. The structure studied has a 15% twin component that is related by a twofold rotation about [100].

Related literature

For 2,4-bis{[bis(trimethylsilyl)amido](diisopropyloamido)phosphido}1,2,3,4-tetraphosphabicyclo(1,1,0)butane, see: Bezombes et al. (2004 ▶). For 2,4-bis(bis-di-tert-butylophosphido)1,2,3,4-tetraphosphabicyclo(1,1,0)butane, see: Matern et al. (1997 ▶). For the handling of twinned diffraction data, see: Spek (2003 ▶).

Experimental

Crystal data

C₂₄H₅₆N₄P₆
M _r = 586.55
Monoclinic,
a = 13.3307 (5) Å
b = 20.9304 (7) Å
c = 12.8939 (5) Å
β = 109.349 (4)°
V = 3394.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 120 (2) K
0.46 × 0.14 × 0.06 mm

Data collection

Oxford Diffraction KM-4 CCD diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.954, T _max = 1.045
6310 measured reflections
6310 independent reflections
4727 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.136
S = 1.04
6310 reflections
324 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808037938/ng2506sup1.cif

e-64-o2427-sup1.cif^{(27KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037938/ng2506Isup2.hkl

e-64-o2427-Isup2.hkl^{(302.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The work was undertaken with financial support from the Polish Ministry of Science and Higher Education (grant No. N N204 271535).

supplementary crystallographic information

Comment

The molecular structure of 1 is shown in Fig.1. The crystal structure of 1 is build up of discrete molecules. The geometry of the phosphorous skeleton in 1 is similar to that in P₄[(NⁱPr₂)(N(SiMe₃)]₂ (Bezombes et al., 2004). The P1—P2 distance, 2.246 (2) Å, and P3—P4 distance, 2.243 (2) Å are slightly longer than P—P distances in the tetraphosphabicyclobutane core (P2,P5,P6,P4). The geometry around N atoms is strictly planar, the sum of angles around N2 atom is 360.8 °. The environments of P1 and P3 atoms are pyramidal, the sum of angles around P1 atom is 310.4 °. Clearly visible is very sharp pyramidal geometry around P2 and P4 atoms, the sum of angles around P2 atom is only 248.81 °.

Experimental

All operations were carried out under purified nitrogen using Schlenk techniques. (ⁱPr₂N)₂PP(SiMe₃)Li 2.5THF (0.170 g, 0.51 mmol) in toluene (5 ml) was dropped slowly to a suspension of Cp^*ZrCl₃(0.484 g, 0.94 mmol) in toluene (4 ml) at -30 °C.The reaction mixture turned immediately brown. The solution was allowed to stand one day at ambient temperature, then evaporated under reduced pressure and dried under vacuum (0.001 Torr) for 1 h. The residue was dissolved in 4 ml pentane and filtered. The solution was kept at 4 °C for two weeks and yielded small amount of colourless crystals of 1.