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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o708.
Published online 2008 March 14. doi:  10.1107/S160053680800665X
PMCID: PMC2960921

1,2,4,5-Tetra­methyl-3,6-diphenyl-1,2,4,5-tetra­aza-3,6-diphosphinane

Abstract

The title compound, C16H22N4P2, crystallizes about a centre of symmetry, leading to a chair conformation of the heterocyclic ring as is commonly found for this type of compound.

Related literature

For related structures, see: Reddy et al. (1994 [triangle], 1995 [triangle]).

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Object name is e-64-0o708-scheme1.jpg

Experimental

Crystal data

  • C16H22N4P2
  • M r = 332.32
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o708-efi1.jpg
  • a = 13.2879 (16) Å
  • b = 7.5426 (9) Å
  • c = 17.125 (2) Å
  • V = 1716.4 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 173 (2) K
  • 0.38 × 0.27 × 0.26 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 10040 measured reflections
  • 1873 independent reflections
  • 1591 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.094
  • S = 1.08
  • 1873 reflections
  • 100 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: SMART-NT (Bruker, 1998 [triangle]); cell refinement: SAINT-Plus (Bruker, 1999 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800665X/tk2250sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800665X/tk2250Isup2.hkl

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

Acknowledgments

The authors thank Project AuTEK (Mintek and Harmony Gold) and the University of the Witwatersrand for financial support.

supplementary crystallographic information

Comment

Compound (I) has a centre of symmetry and the six-membered ring adopts a chair conformation with the phenyl groups on the phosphorous atoms being trans to each other. Reddy et al. (1994) have observed in related compounds, e.g. [HNP(Et)N(Me)]2 and [HNP(Ph)N(Me)]2, that the chair conformation was favoured over the boat conformation and was seen to readily crystallize. Bond lengths and angles in (I), with values for N—N 1.4321 (17), P—N 1.6953 (14) and 1.6984 (12), and P—Carom 1.8412 (15) Å, are in the ranges observed in related structures (Reddy et al., 1994, 1995).

Experimental

In an attempt to crystallize bis(diphenylphosphino)dimethylhydrazine (II) (for synthesis see Reddy et al., 1995), the worked-up diethylether reaction mixture was concentrated and kept at -20 °C for two days. Two small crystals were formed and on analysis of one of the crystals, (I) was identified. Analysis of the 31P NMR spectrum of (II) showed (I) to be present in less than 5%. Further analysis of (I) was not attempted due to the small amount of material available.

Refinement

The H atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H = 0.93 (Ar—H) or 0.96 (CH3) Å, and with Ueq = 1.2 (Ar—H) or 1.5 (CH3) Ueq(C).

Figures

Fig. 1.
Molecular structure of (I) drawn with displacement ellipsoids at the 50% probability level. Hydrogen atoms have been omitted for clarity.

Crystal data

C16H22N4P2F000 = 704
Mr = 332.32Dx = 1.286 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 899 reflections
a = 13.2879 (16) Åθ = 3.0–28.2º
b = 7.5426 (9) ŵ = 0.26 mm1
c = 17.125 (2) ÅT = 173 (2) K
V = 1716.4 (4) Å3Plates, colourless
Z = 40.38 × 0.27 × 0.26 mm

Data collection

Bruker SMART CCD area-detector diffractometer1591 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Monochromator: graphiteθmax = 27.0º
T = 173(2) Kθmin = 2.4º
[var phi] and ω scansh = −15→16
Absorption correction: nonek = −7→9
10040 measured reflectionsl = −21→21
1873 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.094  w = 1/[σ2(Fo2) + (0.0506P)2 + 0.5379P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.005
1873 reflectionsΔρmax = 0.32 e Å3
100 parametersΔρmin = −0.25 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
C1−0.08579 (13)0.3217 (2)−0.05297 (9)0.0359 (4)
H1A−0.03640.4122−0.06240.054*
H1B−0.14420.3737−0.02920.054*
H1C−0.10440.2675−0.10160.054*
C20.17104 (11)−0.0731 (2)−0.08775 (8)0.0336 (3)
H2A0.21380.0277−0.09610.050*
H2B0.1272−0.0878−0.13190.050*
H2C0.2116−0.1775−0.08150.050*
C110.09375 (10)0.14618 (18)0.11718 (8)0.0257 (3)
C120.03662 (11)0.25669 (19)0.16564 (8)0.0295 (3)
H12−0.01270.32880.14380.035*
C130.05251 (13)0.2604 (2)0.24603 (9)0.0339 (3)
H130.01350.33380.27750.041*
C140.12622 (12)0.1549 (2)0.27919 (9)0.0362 (4)
H140.13590.15540.33300.043*
C150.18563 (12)0.0482 (2)0.23183 (9)0.0372 (4)
H150.2359−0.02150.25390.045*
C160.17020 (11)0.0452 (2)0.15125 (9)0.0307 (3)
H160.2112−0.02480.11990.037*
N1−0.04376 (10)0.18785 (15)−0.00091 (7)0.0277 (3)
N20.11088 (9)−0.04525 (16)−0.01743 (7)0.0277 (3)
P10.08233 (3)0.16498 (5)0.01035 (2)0.02618 (14)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0509 (10)0.0263 (8)0.0304 (8)0.0060 (7)−0.0051 (7)0.0052 (6)
C20.0319 (7)0.0386 (8)0.0302 (7)0.0019 (6)0.0104 (6)−0.0022 (6)
C110.0285 (7)0.0237 (7)0.0250 (7)−0.0039 (5)0.0019 (5)0.0006 (5)
C120.0330 (7)0.0262 (7)0.0292 (7)0.0013 (6)0.0007 (6)0.0004 (6)
C130.0375 (8)0.0345 (8)0.0298 (8)−0.0014 (6)0.0017 (6)−0.0076 (7)
C140.0391 (9)0.0413 (9)0.0283 (7)−0.0057 (7)−0.0076 (6)−0.0036 (6)
C150.0339 (8)0.0385 (9)0.0392 (8)0.0016 (7)−0.0129 (6)−0.0017 (7)
C160.0269 (7)0.0306 (7)0.0346 (7)−0.0002 (6)−0.0009 (6)−0.0042 (6)
N10.0323 (6)0.0226 (6)0.0282 (6)0.0037 (5)0.0036 (5)0.0076 (5)
N20.0314 (6)0.0252 (6)0.0265 (6)0.0025 (5)0.0099 (5)0.0015 (5)
P10.0307 (2)0.0230 (2)0.0248 (2)0.00033 (14)0.00652 (14)0.00337 (13)

Geometric parameters (Å, °)

C1—N11.4583 (18)C12—H120.9300
C1—H1A0.9600C13—C141.384 (2)
C1—H1B0.9600C13—H130.9300
C1—H1C0.9600C14—C151.389 (2)
C2—N21.4605 (17)C14—H140.9300
C2—H2A0.9600C15—C161.395 (2)
C2—H2B0.9600C15—H150.9300
C2—H2C0.9600C16—H160.9300
C11—C161.398 (2)N1—N2i1.4321 (17)
C11—C121.400 (2)N1—P11.6953 (14)
C11—P11.8412 (15)N2—N1i1.4321 (17)
C12—C131.393 (2)N2—P11.6984 (12)
N1—C1—H1A109.5C12—C13—H13120.0
N1—C1—H1B109.5C13—C14—C15119.73 (14)
H1A—C1—H1B109.5C13—C14—H14120.1
N1—C1—H1C109.5C15—C14—H14120.1
H1A—C1—H1C109.5C14—C15—C16120.24 (14)
H1B—C1—H1C109.5C14—C15—H15119.9
N2—C2—H2A109.5C16—C15—H15119.9
N2—C2—H2B109.5C15—C16—C11120.72 (14)
H2A—C2—H2B109.5C15—C16—H16119.6
N2—C2—H2C109.5C11—C16—H16119.6
H2A—C2—H2C109.5N2i—N1—C1114.56 (12)
H2B—C2—H2C109.5N2i—N1—P1120.94 (9)
C16—C11—C12118.12 (13)C1—N1—P1121.23 (10)
C16—C11—P1121.12 (11)N1i—N2—C2114.43 (11)
C12—C11—P1119.90 (11)N1i—N2—P1120.04 (9)
C13—C12—C11121.04 (14)C2—N2—P1119.18 (10)
C13—C12—H12119.5N1—P1—N2106.49 (6)
C11—C12—H12119.5N1—P1—C11101.67 (6)
C14—C13—C12120.08 (14)N2—P1—C11100.84 (6)
C14—C13—H13120.0
C16—C11—C12—C13−2.7 (2)N2i—N1—P1—C11−66.99 (11)
P1—C11—C12—C13−172.18 (11)C1—N1—P1—C11134.55 (11)
C11—C12—C13—C140.5 (2)N1i—N2—P1—N1−37.75 (13)
C12—C13—C14—C151.3 (2)C2—N2—P1—N1112.73 (11)
C13—C14—C15—C16−1.0 (2)N1i—N2—P1—C1168.00 (11)
C14—C15—C16—C11−1.3 (2)C2—N2—P1—C11−141.52 (11)
C12—C11—C16—C153.1 (2)C16—C11—P1—N1148.76 (12)
P1—C11—C16—C15172.42 (12)C12—C11—P1—N1−42.10 (12)
N2i—N1—P1—N238.17 (13)C16—C11—P1—N239.20 (13)
C1—N1—P1—N2−120.30 (12)C12—C11—P1—N2−151.65 (11)

Symmetry codes: (i) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2250).

References

  • Bruker (1998). SMART-NT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (1999). SAINT-Plus (includes XPREP and SADABS). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Reddy, V. S., Katti, K. V. & Barnes, C. L. (1994). Chem. Ber.127, 1355–1357.
  • Reddy, V. S., Katti, K. V. & Barnes, C. L. (1995). Inorg. Chem.34, 5483–5488.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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