N,P,P-Triisopropyl­phosphinic amide

Abstract

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 R ₂P(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,

• a = 15.030 (3) Å

• b = 8.4813 (17) Å

• c = 10.071 (2) Å

• β = 107.36 (3)°

• V = 1225.3 (4) ų

• 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[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

H atoms were placed in idealized positions with d(N—H) = 0.88, d(C—H) = 0.98 (CH₃) and 1.00 Å (CH) and refined using a riding model with U_iso(H) fixed at 1.5 U_eq(C) for CH₃ and 1.2 U_eq(C) for NH and CH.

Figures

Fig. 1.

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

Crystal data

C9H22NOP	F(000) = 424
Mr = 191.25	Dx = 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

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

Refinement

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(Fo2) + (0.0547P)2] where P = (Fo2 + 2Fc2)/3
2807 reflections	(Δ/σ)max = 0.001
115 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) x, −y+1/2, z+1/2.