N-(Diphenyl­phosphino­yl)hydroxy­lamine

Blatch, A.J.; Howard, J.A.K.; Probert, M.R.; Whiting, A.

doi:10.1107/S1600536806044862

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 11| November 2006| Pages o5343-o5345

https://doi.org/10.1107/S1600536806044862

N-(Diphenylphosphinoyl)hydroxylamine

Alexandrea J. Blatch,^a Judith A. K. Howard,^a Michael R. Probert ^a and Andrew Whiting ^a ^*

^aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England
^*Correspondence e-mail: andy.whiting@durham.ac.uk

(Received 23 October 2006; accepted 26 October 2006; online 31 October 2006)

The title compound, C₁₂H₁₂NO₂P, is the first structurally studied phosphorus hydroxylamine derivative. The N atom is pyramidal. In the crystal structure, hydrogen bonds link molecules into double ribbons.

Comment

N-(Diphenylphosphinoyl)hydroxylamine, (I), and its analogues with different aryl and alkyl substituents, were synthesized by Harger (1983 ), and it has proved to be a useful intermediate in organic synthesis (Ware & King, 1999 ). No compound of this class has been previously studied by X-ray crystallography.

The molecular structure of (I) is shown in Fig. 1. The N atom is substantially pyramidal: the mean bond angle at it equals 112°. The geometry of the P—NH—OH group resembles that of S—NH—OH in the N-hydroxysulfonamides MeSO₂NHOH (Brink & Mattes, 1986 ) and PhSO₂NHOH (Scholz et al., 1989 ), where the N atom is also pyramidal and the N—O distances are 1.437 (3) and 1.415 (6) Å, respectively. On the other hand, in —C(=O)—NH—OH units, the N atom usually has a planar configuration: out of 47 such structures present in the August 2006 update of the Cambridge Structural Database (Allen, 2002 ), only eight have a substantially pyramidal N atom. An electron-withdrawing hydroxyl group causes a small but significant lengthening of the P—N bond in (I) compared with the values of 1.630 (5) Å in Ph₂P(=O)NH₂ (Oliva et al., 1981 , Schlecht et al., 1998 ) and 1.642 (5) in Ph₂P(=O)NHPh (Priya et al., 2005 ).

The molecule of (I), except for the hydroxyl group and the H atom attached to N, has an approximate local mirror plane which passes through the atoms P, O1 and N. The lone electron pair of the N atom lies in the same plane.

Both the amino and the hydroxyl groups form intermolecular hydrogen bonds with the phosphinoyl atom O2 (Table 2). These bonds link the molecules into an extended double ribbon running parallel to the b axis (Fig. 2).

Figure 1
The molecular structure of (I)

, showing displacement ellipsoids at the 50% probability level.

Figure 2
Part of the crystal structure of (I)

, with hydrogen bonds shown as dashed lines. [Symmetry codes: (i) x, y − 1, z, (ii) 1 − x, y − $[{1\over 2}]$ , 1 − z, (iii) 1 − x, y + $[{1\over 2}]$ , 1 − z, (iv) 1 − x, y − $[{3\over 2}]$ , 1 − z, (v) x, y + 1, z.]

Experimental

To a solution of N,O-bis(trimethylsilyl)hydroxylamine (1.790 g, 9.78 mmol) stirred at 273 K in anhydrous dichloromethane (8 ml), diphenylphosphinic chloride (1.52 ml, 7.83 mmol) was added dropwise. After 30 min, the solution was evaporated, the resulting oily solid resuspended in toluene (6 ml) and the white solid removed by filtration. The resulting solid was redissolved in anhydrous dichloromethane (8 ml) and methanol (0.8 g) and partially evaporated (ca 4 ml) after 1 h. The resulting solid suspension was removed by filtration and purified by recrystallization from methanol, yielding the product, (I), as white crystals (yield 0.953 g, 41.8%). The compound has a m.p. (decomposition) at 400.9–404.7 K. However, although this temperature differs somewhat from the ranges of 418–419 K found by Harger (1983) and 416–418 K by Ware & King (1999), all spectroscopic and analytical properties were identical to those reported by these authors.

Crystal data

C₁₂H₁₂NO₂P
M_r = 233.20
Monoclinic, P 2₁
a = 8.5195 (9) Å
b = 5.7511 (6) Å
c = 11.958 (1) Å
β = 105.32 (1)°
V = 565.1 (1) Å³
Z = 2
D_x = 1.371 Mg m⁻³
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 120 (2) K
Block, colourless
0.3 × 0.2 × 0.18 mm

Data collection

Bruker SMART 6K CCD area-detector diffractometer
ω scans
Absorption correction: none
5264 measured reflections
3112 independent reflections
2826 reflections with I > 2σ(I)
R_int = 0.024
θ_max = 30.0°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.097
S = 0.99
3112 reflections
193 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0525P)² + 0.1713P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ), with 1314 Friedel pairs
Flack parameter: −0.12 (10)

Table 1
Selected geometric parameters (Å, °)

P—O2	1.4965 (15)
P—N	1.6612 (18)
P—C11	1.797 (2)
P—C1	1.797 (2)
O1—N	1.441 (2)
O1—H0	0.78 (4)
N—H1	0.88 (3)

O2—P—N	118.76 (8)
O2—P—C11	110.42 (9)
N—P—C11	103.62 (9)
O2—P—C1	111.73 (9)
N—P—C1	100.79 (9)
C11—P—C1	110.90 (9)
O1—N—P	111.70 (13)
O1—N—H1	105.9 (17)
P—N—H1	116.8 (19)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H0⋯O2ⁱ	0.78 (4)	1.93 (4)	2.685 (2)	163 (3)
N—H1⋯O2ⁱⁱ	0.88 (3)	2.10 (3)	2.945 (2)	160 (2)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

All H atoms were refined in an isotropic approximation, with C—H distances in the range 0.89 (4)–1.01 (3) Å.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806044862/lh2221sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806044862/lh2221Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

N-(diphenylphosphinoyl)hydroxylamine top

Crystal data top

C₁₂H₁₂NO₂P	F(000) = 244
M_r = 233.20	D_x = 1.371 Mg m⁻³
Monoclinic, P2₁	Melting point: 402.8(19) K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.5195 (9) Å	Cell parameters from 2257 reflections
b = 5.7511 (6) Å	θ = 2.5–29.9°
c = 11.958 (1) Å	µ = 0.23 mm⁻¹
β = 105.32 (1)°	T = 120 K
V = 565.1 (1) Å³	Block, colourless
Z = 2	0.3 × 0.2 × 0.18 mm

Data collection top

Bruker SMART CCD 6 K area-detector diffractometer	2826 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 30.0°, θ_min = 1.8°
Detector resolution: 5.6 pixels mm^-1	h = −10→11
ω scans	k = −8→8
5264 measured reflections	l = −16→16
3112 independent reflections

Refinement top

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)] = 0.039	All H-atom parameters refined
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0525P)² + 0.1713P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
3112 reflections	Δρ_max = 0.32 e Å⁻³
193 parameters	Δρ_min = −0.31 e Å⁻³
1 restraint	Absolute structure: Flack (1983), with 1314 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.12 (10)

Special details top

Experimental. The data collection nominally covered a full sphere of reciprocal space, by a combination of 4 runs of narrow-frame ω scans (scan width 0.3° ω, 5 s exposure), every run at a different φ and/or 2θ angle. Crystal to detector distance 4.85 cm. 1798 unique reflections after merging Friedel equivalents.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P	0.49405 (5)	0.54483 (9)	0.31719 (4)	0.01523 (11)
O1	0.34049 (18)	0.1992 (3)	0.37448 (14)	0.0215 (3)
H0	0.352 (3)	0.072 (7)	0.357 (2)	0.032 (8)*
O2	0.41802 (17)	0.7499 (3)	0.35948 (12)	0.0186 (3)
N	0.5009 (2)	0.2928 (3)	0.38621 (15)	0.0181 (3)
H1	0.549 (3)	0.293 (5)	0.461 (2)	0.027 (7)*
C1	0.7066 (2)	0.5917 (3)	0.32967 (16)	0.0173 (4)
C2	0.7774 (2)	0.8000 (4)	0.37769 (17)	0.0199 (4)
H2	0.708 (3)	0.916 (5)	0.407 (2)	0.027 (7)*
C3	0.9428 (3)	0.8397 (4)	0.38948 (18)	0.0225 (4)
H3	0.994 (3)	0.982 (6)	0.421 (2)	0.034 (8)*
C4	1.0360 (3)	0.6723 (4)	0.35245 (19)	0.0243 (4)
H4	1.148 (3)	0.688 (6)	0.357 (2)	0.034 (8)*
C5	0.9659 (3)	0.4657 (4)	0.3037 (2)	0.0246 (4)
H5	1.024 (4)	0.349 (6)	0.279 (3)	0.042 (8)*
C6	0.8007 (2)	0.4248 (4)	0.29228 (18)	0.0202 (4)
H6	0.753 (3)	0.281 (6)	0.261 (2)	0.032 (7)*
C11	0.3864 (2)	0.4761 (4)	0.17032 (17)	0.0188 (4)
C12	0.4124 (3)	0.2693 (4)	0.11705 (19)	0.0237 (4)
H12	0.490 (4)	0.166 (6)	0.161 (3)	0.040 (8)*
C13	0.3292 (3)	0.2269 (5)	0.0022 (2)	0.0303 (5)
H13	0.354 (4)	0.086 (6)	−0.032 (3)	0.042 (9)*
C14	0.2185 (3)	0.3873 (5)	−0.0585 (2)	0.0339 (6)
H14	0.155 (4)	0.361 (7)	−0.133 (3)	0.055 (10)*
C15	0.1895 (3)	0.5920 (5)	−0.0057 (2)	0.0330 (6)
H15	0.114 (4)	0.687 (6)	−0.048 (3)	0.045 (9)*
C16	0.2744 (3)	0.6370 (4)	0.10921 (19)	0.0253 (4)
H16	0.263 (3)	0.778 (6)	0.148 (2)	0.029 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P	0.0159 (2)	0.0138 (2)	0.0163 (2)	0.0000 (2)	0.00476 (15)	−0.0004 (2)
O1	0.0194 (7)	0.0161 (7)	0.0313 (8)	−0.0018 (5)	0.0106 (6)	0.0004 (6)
O2	0.0190 (7)	0.0167 (7)	0.0207 (7)	0.0008 (5)	0.0060 (6)	−0.0018 (6)
N	0.0178 (8)	0.0167 (8)	0.0200 (8)	−0.0019 (6)	0.0055 (6)	0.0017 (6)
C1	0.0167 (8)	0.0200 (11)	0.0149 (8)	−0.0005 (7)	0.0038 (6)	0.0023 (7)
C2	0.0194 (9)	0.0208 (10)	0.0193 (9)	−0.0005 (8)	0.0049 (7)	−0.0009 (8)
C3	0.0225 (10)	0.0242 (10)	0.0197 (9)	−0.0043 (8)	0.0035 (8)	0.0012 (8)
C4	0.0176 (9)	0.0332 (12)	0.0217 (9)	−0.0009 (9)	0.0044 (8)	0.0053 (9)
C5	0.0229 (10)	0.0268 (11)	0.0262 (10)	0.0059 (8)	0.0100 (9)	0.0039 (9)
C6	0.0196 (9)	0.0199 (10)	0.0214 (9)	0.0011 (8)	0.0059 (8)	−0.0010 (8)
C11	0.0184 (9)	0.0206 (9)	0.0172 (8)	−0.0036 (7)	0.0046 (7)	−0.0014 (7)
C12	0.0259 (10)	0.0215 (10)	0.0237 (9)	−0.0018 (8)	0.0068 (8)	−0.0038 (9)
C13	0.0398 (13)	0.0291 (13)	0.0233 (10)	−0.0066 (10)	0.0105 (10)	−0.0098 (9)
C14	0.0402 (13)	0.0418 (15)	0.0167 (9)	−0.0110 (11)	0.0023 (10)	−0.0045 (10)
C15	0.0352 (12)	0.0355 (17)	0.0233 (10)	0.0010 (10)	−0.0013 (9)	0.0059 (10)
C16	0.0288 (11)	0.0237 (10)	0.0220 (10)	0.0005 (9)	0.0044 (9)	0.0020 (9)

Geometric parameters (Å, º) top

P—O2	1.4965 (15)	C5—C6	1.397 (3)
P—N	1.6612 (18)	C5—H5	0.93 (3)
P—C11	1.797 (2)	C6—H6	0.95 (3)
P—C1	1.797 (2)	C11—C16	1.390 (3)
O1—N	1.441 (2)	C11—C12	1.394 (3)
O1—H0	0.78 (4)	C12—C13	1.391 (3)
N—H1	0.88 (3)	C12—H12	0.94 (3)
C1—C2	1.395 (3)	C13—C14	1.380 (4)
C1—C6	1.398 (3)	C13—H13	0.96 (3)
C2—C3	1.397 (3)	C14—C15	1.389 (4)
C2—H2	1.01 (3)	C14—H14	0.92 (4)
C3—C4	1.393 (3)	C15—C16	1.397 (3)
C3—H3	0.96 (3)	C15—H15	0.89 (4)
C4—C5	1.387 (3)	C16—H16	0.95 (3)
C4—H4	0.95 (3)

O2—P—N	118.76 (8)	C4—C5—H5	123 (2)
O2—P—C11	110.42 (9)	C6—C5—H5	117 (2)
N—P—C11	103.62 (9)	C5—C6—C1	120.1 (2)
O2—P—C1	111.73 (9)	C5—C6—H6	120.0 (17)
N—P—C1	100.79 (9)	C1—C6—H6	119.9 (17)
C11—P—C1	110.90 (9)	C16—C11—C12	119.82 (19)
N—O1—H0	101 (2)	C16—C11—P	118.00 (16)
O1—N—P	111.70 (13)	C12—C11—P	122.18 (16)
O1—N—H1	105.9 (17)	C13—C12—C11	120.0 (2)
P—N—H1	116.8 (19)	C13—C12—H12	123 (2)
C2—C1—C6	119.93 (19)	C11—C12—H12	117 (2)
C2—C1—P	118.67 (15)	C14—C13—C12	120.0 (2)
C6—C1—P	121.40 (15)	C14—C13—H13	122.9 (18)
C1—C2—C3	119.8 (2)	C12—C13—H13	117.1 (18)
C1—C2—H2	118.7 (16)	C13—C14—C15	120.4 (2)
C3—C2—H2	121.5 (16)	C13—C14—H14	123 (2)
C4—C3—C2	120.0 (2)	C15—C14—H14	117 (2)
C4—C3—H3	118.5 (17)	C14—C15—C16	119.7 (2)
C2—C3—H3	121.5 (17)	C14—C15—H15	117 (2)
C5—C4—C3	120.4 (2)	C16—C15—H15	123 (2)
C5—C4—H4	115.1 (19)	C11—C16—C15	119.9 (2)
C3—C4—H4	124.4 (19)	C11—C16—H16	116.8 (17)
C4—C5—C6	119.8 (2)	C15—C16—H16	123.2 (17)

O2—P—N—O1	65.74 (16)	C11—P—C1—C6	−54.62 (19)
C11—P—N—O1	−57.12 (15)	O2—P—C11—C16	12.1 (2)
C1—P—N—O1	−171.94 (13)	N—P—C11—C16	140.31 (17)
O2—P—C1—C2	1.63 (18)	C1—P—C11—C16	−112.30 (17)
N—P—C1—C2	−125.48 (16)	O2—P—C11—C12	−168.05 (16)
C11—P—C1—C2	125.29 (16)	N—P—C11—C12	−39.85 (19)
O2—P—C1—C6	−178.28 (15)	C1—P—C11—C12	67.54 (19)
N—P—C1—C6	54.61 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H0···O2ⁱ	0.78 (4)	1.93 (4)	2.685 (2)	163 (3)
N—H1···O2ⁱⁱ	0.88 (3)	2.10 (3)	2.945 (2)	160 (2)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1.

Acknowledgements

The authors thank both the EPSRC and GlaxoSmithKline Pharmaceuticals for a CASE award (to AJB), and Dr A. S. Batsanov for advice.

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