Acta Cryst. (2008). E64, o708 [ doi:10.1107/S160053680800665X ]
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.
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.
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).
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./tk2250fig1thm.gif)
| Fig. 1. Molecular structure of (I) drawn with displacement ellipsoids at the 50% probability level. Hydrogen atoms have been omitted for clarity. |
| C16H22N4P2 | F000 = 704 |
| Mr = 332.32 | Dx = 1.286 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 899 reflections |
| a = 13.2879 (16) Å | θ = 3.0–28.2º |
| b = 7.5426 (9) Å | µ = 0.26 mm−1 |
| c = 17.125 (2) Å | T = 173 (2) K |
| V = 1716.4 (4) Å3 | Plates, colourless |
| Z = 4 | 0.38 × 0.27 × 0.26 mm |
| Bruker SMART CCD area-detector diffractometer | 1591 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.031 |
| Monochromator: graphite | θmax = 27.0º |
| T = 173(2) K | θmin = 2.4º |
| φ and ω scans | h = −15→16 |
| Absorption correction: none | k = −7→9 |
| 10040 measured reflections | l = −21→21 |
| 1873 independent reflections |
| 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)] = 0.030 | H-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 reflections | Δρmax = 0.32 e Å−3 |
| 100 parameters | Δρmin = −0.25 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C16H22N4P2 | V = 1716.4 (4) Å3 |
| Mr = 332.32 | Z = 4 |
| Orthorhombic, Pbca | Mo Kα |
| a = 13.2879 (16) Å | µ = 0.26 mm−1 |
| b = 7.5426 (9) Å | T = 173 (2) K |
| c = 17.125 (2) Å | 0.38 × 0.27 × 0.26 mm |
| Bruker SMART CCD area-detector diffractometer | 1873 independent reflections |
| Absorption correction: none | 1591 reflections with I > 2σ(I) |
| 10040 measured reflections | Rint = 0.031 |
| R[F2 > 2σ(F2)] = 0.030 | 100 parameters |
| wR(F2) = 0.094 | H-atom parameters constrained |
| S = 1.08 | Δρmax = 0.32 e Å−3 |
| 1873 reflections | Δρmin = −0.25 e Å−3 |
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 | ||
| C1 | −0.08579 (13) | 0.3217 (2) | −0.05297 (9) | 0.0359 (4) | |
| H1A | −0.0364 | 0.4122 | −0.0624 | 0.054* | |
| H1B | −0.1442 | 0.3737 | −0.0292 | 0.054* | |
| H1C | −0.1044 | 0.2675 | −0.1016 | 0.054* | |
| C2 | 0.17104 (11) | −0.0731 (2) | −0.08775 (8) | 0.0336 (3) | |
| H2A | 0.2138 | 0.0277 | −0.0961 | 0.050* | |
| H2B | 0.1272 | −0.0878 | −0.1319 | 0.050* | |
| H2C | 0.2116 | −0.1775 | −0.0815 | 0.050* | |
| C11 | 0.09375 (10) | 0.14618 (18) | 0.11718 (8) | 0.0257 (3) | |
| C12 | 0.03662 (11) | 0.25669 (19) | 0.16564 (8) | 0.0295 (3) | |
| H12 | −0.0127 | 0.3288 | 0.1438 | 0.035* | |
| C13 | 0.05251 (13) | 0.2604 (2) | 0.24603 (9) | 0.0339 (3) | |
| H13 | 0.0135 | 0.3338 | 0.2775 | 0.041* | |
| C14 | 0.12622 (12) | 0.1549 (2) | 0.27919 (9) | 0.0362 (4) | |
| H14 | 0.1359 | 0.1554 | 0.3330 | 0.043* | |
| C15 | 0.18563 (12) | 0.0482 (2) | 0.23183 (9) | 0.0372 (4) | |
| H15 | 0.2359 | −0.0215 | 0.2539 | 0.045* | |
| C16 | 0.17020 (11) | 0.0452 (2) | 0.15125 (9) | 0.0307 (3) | |
| H16 | 0.2112 | −0.0248 | 0.1199 | 0.037* | |
| N1 | −0.04376 (10) | 0.18785 (15) | −0.00091 (7) | 0.0277 (3) | |
| N2 | 0.11088 (9) | −0.04525 (16) | −0.01743 (7) | 0.0277 (3) | |
| P1 | 0.08233 (3) | 0.16498 (5) | 0.01035 (2) | 0.02618 (14) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0509 (10) | 0.0263 (8) | 0.0304 (8) | 0.0060 (7) | −0.0051 (7) | 0.0052 (6) |
| C2 | 0.0319 (7) | 0.0386 (8) | 0.0302 (7) | 0.0019 (6) | 0.0104 (6) | −0.0022 (6) |
| C11 | 0.0285 (7) | 0.0237 (7) | 0.0250 (7) | −0.0039 (5) | 0.0019 (5) | 0.0006 (5) |
| C12 | 0.0330 (7) | 0.0262 (7) | 0.0292 (7) | 0.0013 (6) | 0.0007 (6) | 0.0004 (6) |
| C13 | 0.0375 (8) | 0.0345 (8) | 0.0298 (8) | −0.0014 (6) | 0.0017 (6) | −0.0076 (7) |
| C14 | 0.0391 (9) | 0.0413 (9) | 0.0283 (7) | −0.0057 (7) | −0.0076 (6) | −0.0036 (6) |
| C15 | 0.0339 (8) | 0.0385 (9) | 0.0392 (8) | 0.0016 (7) | −0.0129 (6) | −0.0017 (7) |
| C16 | 0.0269 (7) | 0.0306 (7) | 0.0346 (7) | −0.0002 (6) | −0.0009 (6) | −0.0042 (6) |
| N1 | 0.0323 (6) | 0.0226 (6) | 0.0282 (6) | 0.0037 (5) | 0.0036 (5) | 0.0076 (5) |
| N2 | 0.0314 (6) | 0.0252 (6) | 0.0265 (6) | 0.0025 (5) | 0.0099 (5) | 0.0015 (5) |
| P1 | 0.0307 (2) | 0.0230 (2) | 0.0248 (2) | 0.00033 (14) | 0.00652 (14) | 0.00337 (13) |
| C1—N1 | 1.4583 (18) | C12—H12 | 0.9300 |
| C1—H1A | 0.9600 | C13—C14 | 1.384 (2) |
| C1—H1B | 0.9600 | C13—H13 | 0.9300 |
| C1—H1C | 0.9600 | C14—C15 | 1.389 (2) |
| C2—N2 | 1.4605 (17) | C14—H14 | 0.9300 |
| C2—H2A | 0.9600 | C15—C16 | 1.395 (2) |
| C2—H2B | 0.9600 | C15—H15 | 0.9300 |
| C2—H2C | 0.9600 | C16—H16 | 0.9300 |
| C11—C16 | 1.398 (2) | N1—N2i | 1.4321 (17) |
| C11—C12 | 1.400 (2) | N1—P1 | 1.6953 (14) |
| C11—P1 | 1.8412 (15) | N2—N1i | 1.4321 (17) |
| C12—C13 | 1.393 (2) | N2—P1 | 1.6984 (12) |
| N1—C1—H1A | 109.5 | C12—C13—H13 | 120.0 |
| N1—C1—H1B | 109.5 | C13—C14—C15 | 119.73 (14) |
| H1A—C1—H1B | 109.5 | C13—C14—H14 | 120.1 |
| N1—C1—H1C | 109.5 | C15—C14—H14 | 120.1 |
| H1A—C1—H1C | 109.5 | C14—C15—C16 | 120.24 (14) |
| H1B—C1—H1C | 109.5 | C14—C15—H15 | 119.9 |
| N2—C2—H2A | 109.5 | C16—C15—H15 | 119.9 |
| N2—C2—H2B | 109.5 | C15—C16—C11 | 120.72 (14) |
| H2A—C2—H2B | 109.5 | C15—C16—H16 | 119.6 |
| N2—C2—H2C | 109.5 | C11—C16—H16 | 119.6 |
| H2A—C2—H2C | 109.5 | N2i—N1—C1 | 114.56 (12) |
| H2B—C2—H2C | 109.5 | N2i—N1—P1 | 120.94 (9) |
| C16—C11—C12 | 118.12 (13) | C1—N1—P1 | 121.23 (10) |
| C16—C11—P1 | 121.12 (11) | N1i—N2—C2 | 114.43 (11) |
| C12—C11—P1 | 119.90 (11) | N1i—N2—P1 | 120.04 (9) |
| C13—C12—C11 | 121.04 (14) | C2—N2—P1 | 119.18 (10) |
| C13—C12—H12 | 119.5 | N1—P1—N2 | 106.49 (6) |
| C11—C12—H12 | 119.5 | N1—P1—C11 | 101.67 (6) |
| C14—C13—C12 | 120.08 (14) | N2—P1—C11 | 100.84 (6) |
| C14—C13—H13 | 120.0 | ||
| C16—C11—C12—C13 | −2.7 (2) | N2i—N1—P1—C11 | −66.99 (11) |
| P1—C11—C12—C13 | −172.18 (11) | C1—N1—P1—C11 | 134.55 (11) |
| C11—C12—C13—C14 | 0.5 (2) | N1i—N2—P1—N1 | −37.75 (13) |
| C12—C13—C14—C15 | 1.3 (2) | C2—N2—P1—N1 | 112.73 (11) |
| C13—C14—C15—C16 | −1.0 (2) | N1i—N2—P1—C11 | 68.00 (11) |
| C14—C15—C16—C11 | −1.3 (2) | C2—N2—P1—C11 | −141.52 (11) |
| C12—C11—C16—C15 | 3.1 (2) | C16—C11—P1—N1 | 148.76 (12) |
| P1—C11—C16—C15 | 172.42 (12) | C12—C11—P1—N1 | −42.10 (12) |
| N2i—N1—P1—N2 | 38.17 (13) | C16—C11—P1—N2 | 39.20 (13) |
| C1—N1—P1—N2 | −120.30 (12) | C12—C11—P1—N2 | −151.65 (11) |
| Symmetry codes: (i) −x, −y, −z. |
The authors thank Project AuTEK (Mintek and Harmony Gold) and the University of the Witwatersrand for financial support.
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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).