N,P,P-Triisopropyl­phosphinic amide

Peulecke, N.; Aluri, B.R.; Müller, B.H.; Spannenberg, A.; Rosenthal, U.

doi:10.1107/S1600536811018551

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1474

doi:10.1107/S1600536811018551

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N,P,P-Triisopropylphosphinic amide

Normen Peulecke,^a ^* Bhaskar R. Aluri,^a Bernd H. Müller,^a Anke Spannenberg ^a and Uwe Rosenthal ^a

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock, Germany
^*Correspondence e-mail: normen.peulecke@catalysis.de

(Received 4 May 2011; accepted 16 May 2011; online 20 May 2011)

The title compound, C₉H₂₂NOP, was obtained by slow diffusion of oxygen into a toluene solution of ⁱPr₂PNHⁱPr. In the crystal, an intermolecular N—H⋯O hydrogen bond occurs.

Related literature

For the synthesis of the starting compound (ⁱPr)₂PNHⁱPr, see: Kuchen et al. (1990 ). For a similar synthesis of the title compound, see: Brück et al. (1995 ). For similar structures of R₂P(O)NHR in which the P atom has at least one attached alkyl substituent, see: Burns et al. (1997 ); Denmark & Dorow (2002 ); Kolodiazhnyi et al. (2003 ); Francesco et al. (2010 ).

Experimental

Crystal data

C₉H₂₂NOP
M_r = 191.25
Monoclinic, P 2₁ /c
a = 15.030 (3) Å
b = 8.4813 (17) Å
c = 10.071 (2) Å
β = 107.36 (3)°
V = 1225.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 195 K
0.42 × 0.26 × 0.20 mm

Data collection

Stoe IPDS II diffractometer
19581 measured reflections
2807 independent reflections
2012 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.091
S = 0.89
2807 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.88	1.98	2.8344 (17)	165
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2005 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018551/yk2008sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018551/yk2008Isup2.hkl

checkCIF report

Comment top

Aminophosphines with alkyl-substituents undergo oxidation very easily compared to their analogue aryl-substituted species. Most of the structurally characterized P,P-diorganylphosphinic amides R¹R²P(O)NHR³ have a sterogenic phosphorus or nitrogen centre (Burns et al., 1997, Denmark et al., 2002, Kolodiazhnyi et al., 2003 and Francesco et al., 2010). Here we report about the structural characterization of the known compound (ⁱPr)₂P(O)N(H)ⁱPr (Fig. 1). The P1—O1 distance is with 1.4799 (11) Å in the range of a P═O double bond. A strong intermolecular hydrogen bond N1—H1A···O1 (N1···O1 2.834 (2), H1A···O1 1.98 Å and N1—H1A···O1 165°) was observed.

Related literature top

For the synthesis of the starting compound (ⁱPr)₂PNHⁱPr, see: Kuchen et al. (1990). For a similar synthesis of the title compound, see: Brück et al. (1995). For similar structures of R₂P(O)NHR in which the phosporus has at least one alkyl moiety, see: Burns et al. (1997); Denmark & Dorow (2002); Kolodiazhnyi et al. (2003); Francesco et al. (2010).

Experimental top

A toluene solution (20 mL) of 0.4 g (2.3 mmol) (ⁱPr)₂PN(H)ⁱPr (Kuchen et al., 1990) was exposed to dry air over a period of 48 h. After evaporation of the solvent, the oily residue was dissolved in n-hexane, filtrated and stored at -40°C for crystallization. After 3 days colourless crystals were formed, which were suitable for X-ray analysis. The analytical data of C₉H₂₂NOP correlated with those in the literature (Brück et al., 1995).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

N,P,P-Triisopropylphosphinic amide top

Crystal data top

C₉H₂₂NOP	F(000) = 424
M_r = 191.25	D_x = 1.037 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5563 reflections
a = 15.030 (3) Å	θ = 2.1–29.2°
b = 8.4813 (17) Å	µ = 0.19 mm⁻¹
c = 10.071 (2) Å	T = 195 K
β = 107.36 (3)°	Prism, colourless
V = 1225.3 (4) Å³	0.42 × 0.26 × 0.20 mm
Z = 4

Data collection top

Stoe IPDS II diffractometer	2012 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.5°, θ_min = 2.8°
ω scans	h = −19→19
19581 measured reflections	k = −11→11
2807 independent reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 0.89	w = 1/[σ²(F_o²) + (0.0547P)²] where P = (F_o² + 2F_c²)/3
2807 reflections	(Δ/σ)_max = 0.001
115 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₉H₂₂NOP	V = 1225.3 (4) Å³
M_r = 191.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.030 (3) Å	µ = 0.19 mm⁻¹
b = 8.4813 (17) Å	T = 195 K
c = 10.071 (2) Å	0.42 × 0.26 × 0.20 mm
β = 107.36 (3)°

Data collection top

Stoe IPDS II diffractometer	2012 reflections with I > 2σ(I)
19581 measured reflections	R_int = 0.035
2807 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 0.89	Δρ_max = 0.39 e Å⁻³
2807 reflections	Δρ_min = −0.16 e Å⁻³
115 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

	x	y	z	U_iso*/U_eq
C1	0.70679 (12)	0.5276 (2)	0.6731 (2)	0.0525 (4)
H1B	0.6513	0.5582	0.5941	0.063*
C2	0.68976 (19)	0.5848 (2)	0.8073 (3)	0.0830 (7)
H2A	0.7434	0.5574	0.8868	0.125*
H2B	0.6336	0.5342	0.8178	0.125*
H2C	0.6813	0.6995	0.8034	0.125*
C3	0.79173 (16)	0.6067 (3)	0.6497 (3)	0.0802 (7)
H3A	0.7812	0.7207	0.6396	0.120*
H3B	0.8021	0.5645	0.5650	0.120*
H3C	0.8466	0.5858	0.7294	0.120*
C4	0.61524 (11)	0.22776 (19)	0.69367 (17)	0.0418 (4)
H4	0.6119	0.2607	0.7874	0.050*
C5	0.52745 (12)	0.2872 (3)	0.5848 (2)	0.0653 (6)
H5A	0.5320	0.2652	0.4915	0.098*
H5B	0.5213	0.4010	0.5960	0.098*
H5C	0.4727	0.2333	0.5971	0.098*
C6	0.62213 (15)	0.0496 (2)	0.6924 (2)	0.0692 (6)
H6A	0.5651	0.0034	0.7039	0.104*
H6B	0.6759	0.0151	0.7689	0.104*
H6C	0.6298	0.0150	0.6037	0.104*
C7	0.89734 (10)	0.2189 (2)	0.79953 (16)	0.0427 (4)
H7	0.9106	0.2800	0.7226	0.051*
C8	0.96785 (13)	0.2667 (3)	0.9330 (2)	0.0733 (6)
H8A	0.9625	0.3801	0.9478	0.110*
H8B	1.0306	0.2429	0.9282	0.110*
H8C	0.9566	0.2083	1.0104	0.110*
C9	0.90379 (17)	0.0463 (3)	0.7687 (3)	0.0834 (7)
H9A	0.8915	−0.0166	0.8429	0.125*
H9B	0.9664	0.0226	0.7633	0.125*
H9C	0.8576	0.0206	0.6797	0.125*
N1	0.80376 (9)	0.26201 (16)	0.80317 (13)	0.0398 (3)
H1A	0.7925	0.2590	0.8840	0.048*
O1	0.73426 (8)	0.26804 (15)	0.53446 (11)	0.0531 (3)
P1	0.71920 (3)	0.31507 (5)	0.66763 (4)	0.03470 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0490 (10)	0.0468 (9)	0.0619 (11)	0.0063 (8)	0.0167 (9)	0.0155 (9)
C2	0.1089 (19)	0.0465 (12)	0.1096 (19)	0.0121 (12)	0.0570 (16)	−0.0108 (12)
C3	0.0785 (15)	0.0565 (13)	0.112 (2)	−0.0137 (11)	0.0373 (14)	0.0151 (12)
C4	0.0398 (8)	0.0532 (10)	0.0348 (8)	−0.0039 (7)	0.0148 (7)	0.0047 (7)
C5	0.0366 (9)	0.0924 (16)	0.0629 (12)	−0.0074 (9)	0.0087 (8)	0.0160 (11)
C6	0.0697 (13)	0.0576 (12)	0.0814 (15)	−0.0150 (10)	0.0243 (12)	0.0030 (10)
C7	0.0377 (8)	0.0581 (11)	0.0365 (8)	0.0107 (7)	0.0174 (7)	0.0075 (7)
C8	0.0426 (10)	0.1149 (19)	0.0573 (12)	0.0060 (11)	0.0072 (9)	−0.0030 (12)
C9	0.0787 (15)	0.0704 (15)	0.1029 (19)	0.0283 (12)	0.0297 (14)	−0.0056 (13)
N1	0.0383 (7)	0.0593 (8)	0.0250 (6)	0.0094 (6)	0.0143 (5)	0.0085 (6)
O1	0.0553 (7)	0.0817 (9)	0.0270 (6)	0.0022 (6)	0.0193 (5)	0.0009 (5)
P1	0.03607 (19)	0.0451 (2)	0.02528 (19)	0.00340 (18)	0.01274 (14)	0.00474 (18)

Geometric parameters (Å, º) top

C1—C3	1.521 (3)	C6—H6A	0.9800
C1—C2	1.528 (3)	C6—H6B	0.9800
C1—P1	1.8150 (18)	C6—H6C	0.9800
C1—H1B	1.0000	C7—N1	1.4644 (19)
C2—H2A	0.9800	C7—C8	1.498 (3)
C2—H2B	0.9800	C7—C9	1.505 (3)
C2—H2C	0.9800	C7—H7	1.0000
C3—H3A	0.9800	C8—H8A	0.9800
C3—H3B	0.9800	C8—H8B	0.9800
C3—H3C	0.9800	C8—H8C	0.9800
C4—C6	1.515 (3)	C9—H9A	0.9800
C4—C5	1.527 (2)	C9—H9B	0.9800
C4—P1	1.8175 (16)	C9—H9C	0.9800
C4—H4	1.0000	N1—P1	1.6265 (14)
C5—H5A	0.9800	N1—H1A	0.8800
C5—H5B	0.9800	O1—P1	1.4799 (11)
C5—H5C	0.9800

C3—C1—C2	111.54 (18)	H6A—C6—H6B	109.5
C3—C1—P1	109.54 (13)	C4—C6—H6C	109.5
C2—C1—P1	112.84 (13)	H6A—C6—H6C	109.5
C3—C1—H1B	107.6	H6B—C6—H6C	109.5
C2—C1—H1B	107.6	N1—C7—C8	109.72 (14)
P1—C1—H1B	107.6	N1—C7—C9	111.68 (15)
C1—C2—H2A	109.5	C8—C7—C9	112.11 (17)
C1—C2—H2B	109.5	N1—C7—H7	107.7
H2A—C2—H2B	109.5	C8—C7—H7	107.7
C1—C2—H2C	109.5	C9—C7—H7	107.7
H2A—C2—H2C	109.5	C7—C8—H8A	109.5
H2B—C2—H2C	109.5	C7—C8—H8B	109.5
C1—C3—H3A	109.5	H8A—C8—H8B	109.5
C1—C3—H3B	109.5	C7—C8—H8C	109.5
H3A—C3—H3B	109.5	H8A—C8—H8C	109.5
C1—C3—H3C	109.5	H8B—C8—H8C	109.5
H3A—C3—H3C	109.5	C7—C9—H9A	109.5
H3B—C3—H3C	109.5	C7—C9—H9B	109.5
C6—C4—C5	111.69 (16)	H9A—C9—H9B	109.5
C6—C4—P1	109.96 (12)	C7—C9—H9C	109.5
C5—C4—P1	110.96 (11)	H9A—C9—H9C	109.5
C6—C4—H4	108.0	H9B—C9—H9C	109.5
C5—C4—H4	108.0	C7—N1—P1	124.33 (10)
P1—C4—H4	108.0	C7—N1—H1A	117.8
C4—C5—H5A	109.5	P1—N1—H1A	117.8
C4—C5—H5B	109.5	O1—P1—N1	113.17 (7)
H5A—C5—H5B	109.5	O1—P1—C1	109.89 (8)
C4—C5—H5C	109.5	N1—P1—C1	108.11 (8)
H5A—C5—H5C	109.5	O1—P1—C4	113.05 (8)
H5B—C5—H5C	109.5	N1—P1—C4	104.85 (7)
C4—C6—H6A	109.5	C1—P1—C4	107.44 (8)
C4—C6—H6B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	1.98	2.8344 (17)	165

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₂₂NOP
M_r	191.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	195
a, b, c (Å)	15.030 (3), 8.4813 (17), 10.071 (2)
β (°)	107.36 (3)
V (Å³)	1225.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.42 × 0.26 × 0.20

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	19581, 2807, 2012
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.091, 0.89
No. of reflections	2807
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.16

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	1.98	2.8344 (17)	165

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

This work was supported by the Leibniz-Institut für Katalyse e. V. an der Universität Rostock.

References

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