{[N-Benzyl-N-(2-pyridyl)­amino]­methyl­ene}di­phenyl­phosphine oxide

Cui, D.-J.; Zeng, X.-S.; Leng, X.-B.; Xu, F.-B.; Zhang, Z.-Z.

doi:10.1107/S1600536803008304

{[N-Benzyl-N-(2-pyridyl)amino]methylene}diphenylphosphine oxide

D.-J. Cui, X.-S. Zeng, X.-B. Leng, F.-B. Xu and Z.-Z. Zhang

The title compound, Ph₂P(O)CH₂N(CH₂Ph)C₅H₄N or C₂₅H₂₃N₂OP, was obtained by reaction of Ph₂PCH₂N(CH₂Ph)C₅H₄N and H₂O₂. The crystal structure shows distorted tetrahedral geometry around the P atom.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008304/ac6034sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008304/ac6034Isup2.hkl Contains datablock I

CCDC reference: 214625

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Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.047
wR factor = 0.120
Data-to-parameter ratio = 14.2

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No syntax errors found

ADDSYM reports no extra symmetry

Comment top

Pyridylphosphines continue to induce much interest as excellent ligands for stabilizing many transition-metal coordination and organometallic complexes (Espinet & Soulantica, 1999). One important property of these ligands is that they can stabilize metal ions in a variety of valence states and geometries. Hence, a metal–metal bond between an electron-rich metal (soft base) and a high oxidation-state metal (Lewis acid) is easily formed (Zhang & Cheng, 1996). Recently, we designed and synthesized a hetero-binuclear complex containing an Fe—Cu bond by a new pyridylphosphine ligand, viz. Ph₂PCH₂N(c—C₆H₁₁)C₅H₄N (Cui et al., 2001).

Pyridylphosphine oxides have recently been shown to behave either as N(pyridyl)-donor or N(pyridyl),O-chelating ligands upon complexation palladium(II) and platinum(II) centres (Minghetti et al., 1998; Smith et al., 2000). In order to study the interesting coordination ability in this kind of ligand we synthesized a new pyridylphosphine oxide Ph₂P(O)CH₂N(CH₂Ph)C₅H₄N and its molecular structure was determined by the X-ray diffraction study. The X-ray structure of the title compound, (I), shows distorted tetrahedral geometry around P atom. The P—O distance [1.4815 (18) Å] is shorter than those in other triarylphosphine oxides (Smith et al., 2000; Minghetti et al., 1998; Szlyk et al., 1989; Bandoli et al., 1970).

Experimental top

The synthesis of (I) was carried out under an argon atmosphere. To a solution of Ph₂PCH₂N(CH₂Ph)C₅H₄N (0.100 g, 0.252 mmol) in tetrahydrofuran (2 ml) was added aqueous H₂O₂ solution (30% w/w, 0.2 ml). The resulting solution was stirred for about 48 h, filtered to remove some insoluble material and diethyl ether (15 ml) added. The white solid was collected by filtration and dried in vacuo.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998) and SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. A view of (I) along with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing arrangement in a cell of crystal (I).

{[N-Benzyl-N-(2-pyridyl)amino]methylene}diphenylphosphine oxide top

Crystal data top

C₂₅H₂₃N₂OP	F(000) = 840
M_r = 398.42	D_x = 1.250 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.256 (3) Å	Cell parameters from 573 reflections
b = 14.834 (5) Å	θ = 1.9–25.0°
c = 15.957 (5) Å	µ = 0.15 mm⁻¹
β = 104.979 (6)°	T = 293 K
V = 2116.5 (12) Å³	Plate, white
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3727 independent reflections
Radiation source: fine-focus sealed tube	2051 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→7
T_min = 0.971, T_max = 0.985	k = −17→15
8613 measured reflections	l = −18→18

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.05P)²] where P = (F_o² + 2F_c²)/3
3727 reflections	(Δ/σ)_max = 0.009
262 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₅H₂₃N₂OP	V = 2116.5 (12) Å³
M_r = 398.42	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.256 (3) Å	µ = 0.15 mm⁻¹
b = 14.834 (5) Å	T = 293 K
c = 15.957 (5) Å	0.20 × 0.15 × 0.10 mm
β = 104.979 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3727 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2051 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.985	R_int = 0.062
8613 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 0.97	Δρ_max = 0.31 e Å⁻³
3727 reflections	Δρ_min = −0.26 e Å⁻³
262 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
P1	0.94766 (7)	0.82149 (5)	0.17049 (5)	0.0462 (2)
O1	1.07959 (19)	0.86319 (13)	0.14963 (12)	0.0610 (5)
N1	0.7482 (2)	0.95767 (14)	0.10903 (14)	0.0474 (6)
N2	0.5294 (2)	0.92851 (16)	0.15003 (14)	0.0541 (6)
C1	0.9408 (3)	0.70132 (18)	0.15094 (16)	0.0452 (7)
C2	0.8295 (3)	0.64515 (19)	0.16542 (17)	0.0565 (8)
H2A	0.7535	0.6694	0.1868	0.068*
C3	0.8303 (4)	0.5541 (2)	0.14860 (19)	0.0663 (9)
H3A	0.7544	0.5175	0.1580	0.080*
C4	0.9415 (5)	0.5175 (2)	0.1183 (2)	0.0790 (10)
H4A	0.9426	0.4559	0.1079	0.095*
C5	1.0525 (4)	0.5717 (3)	0.1030 (2)	0.0827 (11)
H5A	1.1279	0.5466	0.0815	0.099*
C6	1.0526 (3)	0.6642 (2)	0.11949 (18)	0.0642 (8)
H6A	1.1281	0.7006	0.1093	0.077*
C7	0.9490 (3)	0.83949 (16)	0.28216 (17)	0.0446 (7)
C8	0.8315 (3)	0.81862 (18)	0.3181 (2)	0.0559 (7)
H8A	0.7420	0.7971	0.2826	0.067*
C9	0.8460 (4)	0.8295 (2)	0.4062 (2)	0.0705 (9)
H9A	0.7669	0.8148	0.4297	0.085*
C10	0.9767 (4)	0.8619 (2)	0.4584 (2)	0.0834 (11)
H10A	0.9870	0.8682	0.5177	0.100*
C11	1.0927 (4)	0.8849 (2)	0.4240 (2)	0.0823 (10)
H11A	1.1806	0.9082	0.4597	0.099*
C12	1.0794 (3)	0.8738 (2)	0.33689 (19)	0.0628 (8)
H12A	1.1588	0.8896	0.3141	0.075*
C13	0.7705 (3)	0.86041 (17)	0.10364 (17)	0.0483 (7)
H13A	0.7637	0.8446	0.0438	0.058*
H13B	0.6907	0.8293	0.1209	0.058*
C14	0.6136 (3)	0.98871 (18)	0.12174 (16)	0.0436 (7)
C15	0.5704 (3)	1.07848 (19)	0.10800 (17)	0.0532 (7)
H15A	0.6298	1.1192	0.0876	0.064*
C16	0.4399 (3)	1.1063 (2)	0.12471 (19)	0.0658 (9)
H16A	0.4104	1.1663	0.1165	0.079*
C17	0.3527 (3)	1.0449 (3)	0.1538 (2)	0.0694 (9)
H17A	0.2632	1.0620	0.1655	0.083*
C18	0.4018 (3)	0.9581 (2)	0.16479 (19)	0.0670 (9)
H18A	0.3423	0.9165	0.1839	0.080*
C19	0.8318 (3)	1.01498 (18)	0.06454 (17)	0.0530 (7)
H19A	0.7622	1.0412	0.0143	0.064*
H19B	0.9008	0.9775	0.0435	0.064*
C20	0.9192 (3)	1.09025 (17)	0.11787 (18)	0.0445 (7)
C21	0.9669 (3)	1.16101 (19)	0.0744 (2)	0.0580 (8)
H21A	0.9406	1.1622	0.0141	0.070*
C22	1.0529 (4)	1.2294 (2)	0.1205 (3)	0.0770 (10)
H22A	1.0854	1.2761	0.0909	0.092*
C23	1.0911 (4)	1.2291 (2)	0.2091 (3)	0.0821 (11)
H23A	1.1494	1.2754	0.2397	0.098*
C24	1.0433 (3)	1.1607 (2)	0.2531 (2)	0.0742 (10)
H24A	1.0678	1.1610	0.3134	0.089*
C25	0.9581 (3)	1.0908 (2)	0.20716 (19)	0.0572 (8)
H25A	0.9271	1.0439	0.2371	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0439 (4)	0.0426 (4)	0.0509 (5)	−0.0024 (3)	0.0101 (3)	−0.0008 (4)
O1	0.0503 (11)	0.0663 (14)	0.0694 (13)	−0.0141 (10)	0.0212 (10)	0.0018 (11)
N1	0.0518 (14)	0.0347 (14)	0.0572 (15)	−0.0018 (10)	0.0169 (11)	0.0004 (11)
N2	0.0443 (14)	0.0582 (16)	0.0584 (16)	−0.0001 (12)	0.0108 (12)	0.0099 (12)
C1	0.0504 (17)	0.0426 (17)	0.0410 (16)	0.0075 (13)	0.0089 (13)	−0.0004 (13)
C2	0.067 (2)	0.0463 (19)	0.0536 (18)	0.0000 (15)	0.0110 (15)	−0.0060 (15)
C3	0.091 (2)	0.044 (2)	0.060 (2)	−0.0029 (17)	0.0115 (18)	−0.0073 (16)
C4	0.118 (3)	0.044 (2)	0.067 (2)	0.011 (2)	0.010 (2)	−0.0079 (18)
C5	0.097 (3)	0.075 (3)	0.076 (3)	0.036 (2)	0.023 (2)	−0.011 (2)
C6	0.070 (2)	0.061 (2)	0.061 (2)	0.0087 (16)	0.0161 (16)	−0.0024 (17)
C7	0.0465 (16)	0.0351 (16)	0.0500 (17)	−0.0031 (12)	0.0087 (13)	0.0001 (13)
C8	0.0616 (19)	0.0434 (18)	0.064 (2)	−0.0003 (14)	0.0182 (15)	−0.0047 (16)
C9	0.087 (3)	0.061 (2)	0.074 (2)	0.0002 (18)	0.039 (2)	0.0012 (19)
C10	0.102 (3)	0.093 (3)	0.052 (2)	0.001 (2)	0.015 (2)	−0.006 (2)
C11	0.081 (3)	0.096 (3)	0.062 (2)	−0.017 (2)	0.005 (2)	−0.012 (2)
C12	0.062 (2)	0.066 (2)	0.057 (2)	−0.0065 (16)	0.0097 (16)	−0.0044 (17)
C13	0.0517 (17)	0.0371 (16)	0.0525 (17)	−0.0040 (12)	0.0070 (13)	−0.0005 (13)
C14	0.0422 (16)	0.0440 (18)	0.0393 (16)	−0.0028 (13)	0.0008 (13)	0.0012 (13)
C15	0.0527 (18)	0.0458 (18)	0.0534 (18)	0.0038 (14)	0.0000 (14)	−0.0005 (15)
C16	0.059 (2)	0.058 (2)	0.065 (2)	0.0117 (17)	−0.0108 (17)	−0.0104 (17)
C17	0.0501 (19)	0.084 (3)	0.068 (2)	0.0116 (19)	0.0041 (16)	−0.0053 (19)
C18	0.049 (2)	0.082 (3)	0.068 (2)	−0.0062 (17)	0.0107 (16)	0.0095 (18)
C19	0.0655 (19)	0.0456 (18)	0.0533 (18)	−0.0041 (14)	0.0251 (15)	−0.0014 (14)
C20	0.0443 (16)	0.0389 (17)	0.0552 (19)	0.0009 (12)	0.0220 (14)	−0.0042 (14)
C21	0.0567 (18)	0.052 (2)	0.070 (2)	0.0024 (15)	0.0251 (16)	0.0086 (16)
C22	0.071 (2)	0.049 (2)	0.115 (3)	−0.0108 (17)	0.032 (2)	0.002 (2)
C23	0.067 (2)	0.064 (3)	0.116 (3)	−0.0192 (18)	0.024 (2)	−0.026 (2)
C24	0.064 (2)	0.090 (3)	0.068 (2)	−0.0114 (19)	0.0168 (17)	−0.029 (2)
C25	0.063 (2)	0.056 (2)	0.057 (2)	−0.0102 (15)	0.0237 (15)	−0.0038 (16)

Geometric parameters (Å, º) top

P1—O1	1.4815 (18)	C7—C12	1.390 (3)
P1—C7	1.799 (3)	C8—C9	1.387 (4)
P1—C13	1.804 (2)	C9—C10	1.367 (4)
P1—C1	1.808 (3)	C10—C11	1.370 (4)
N1—C14	1.391 (3)	C11—C12	1.374 (4)
N1—C19	1.452 (3)	C14—C15	1.392 (4)
N1—C13	1.463 (3)	C15—C16	1.366 (4)
N2—C18	1.337 (3)	C16—C17	1.375 (4)
N2—C14	1.338 (3)	C17—C18	1.362 (4)
C1—C6	1.376 (4)	C19—C20	1.507 (3)
C1—C2	1.390 (4)	C20—C25	1.376 (3)
C2—C3	1.378 (4)	C20—C21	1.391 (3)
C3—C4	1.359 (4)	C21—C22	1.378 (4)
C4—C5	1.375 (5)	C22—C23	1.367 (4)
C5—C6	1.398 (4)	C23—C24	1.370 (4)
C7—C8	1.389 (4)	C24—C25	1.391 (4)

O1—P1—C7	111.44 (11)	C10—C9—C8	119.9 (3)
O1—P1—C13	114.16 (12)	C9—C10—C11	120.3 (3)
C7—P1—C13	108.12 (12)	C10—C11—C12	120.1 (3)
O1—P1—C1	111.55 (12)	C11—C12—C7	121.1 (3)
C7—P1—C1	107.96 (12)	N1—C13—P1	113.68 (17)
C13—P1—C1	103.14 (12)	N2—C14—C15	121.5 (3)
C14—N1—C19	119.2 (2)	N2—C14—N1	116.7 (2)
C14—N1—C13	118.7 (2)	C15—C14—N1	121.7 (3)
C19—N1—C13	116.6 (2)	C16—C15—C14	119.4 (3)
C18—N2—C14	117.3 (3)	C15—C16—C17	119.4 (3)
C6—C1—C2	118.7 (3)	C18—C17—C16	117.7 (3)
C6—C1—P1	117.4 (2)	N2—C18—C17	124.7 (3)
C2—C1—P1	123.9 (2)	N1—C19—C20	115.7 (2)
C3—C2—C1	121.0 (3)	C25—C20—C21	118.6 (3)
C4—C3—C2	120.2 (3)	C25—C20—C19	123.2 (2)
C3—C4—C5	120.0 (3)	C21—C20—C19	118.1 (3)
C4—C5—C6	120.3 (3)	C22—C21—C20	120.3 (3)
C1—C6—C5	119.8 (3)	C23—C22—C21	120.6 (3)
C8—C7—C12	117.9 (3)	C22—C23—C24	120.1 (3)
C8—C7—P1	124.7 (2)	C23—C24—C25	119.7 (3)
C12—C7—P1	117.4 (2)	C20—C25—C24	120.7 (3)
C9—C8—C7	120.7 (3)

O1—P1—C1—C6	−0.7 (2)	C19—N1—C13—P1	74.4 (3)
C7—P1—C1—C6	−123.4 (2)	O1—P1—C13—N1	−59.4 (2)
C13—P1—C1—C6	122.3 (2)	C7—P1—C13—N1	65.2 (2)
O1—P1—C1—C2	179.6 (2)	C1—P1—C13—N1	179.41 (19)
C7—P1—C1—C2	56.9 (2)	C18—N2—C14—C15	−0.1 (4)
C13—P1—C1—C2	−57.4 (2)	C18—N2—C14—N1	178.2 (2)
C6—C1—C2—C3	−0.1 (4)	C19—N1—C14—N2	169.4 (2)
P1—C1—C2—C3	179.6 (2)	C13—N1—C14—N2	16.6 (3)
C1—C2—C3—C4	0.7 (4)	C19—N1—C14—C15	−12.2 (4)
C2—C3—C4—C5	−1.0 (5)	C13—N1—C14—C15	−165.1 (2)
C3—C4—C5—C6	0.8 (5)	N2—C14—C15—C16	0.8 (4)
C2—C1—C6—C5	−0.1 (4)	N1—C14—C15—C16	−177.4 (2)
P1—C1—C6—C5	−179.8 (2)	C14—C15—C16—C17	−0.8 (4)
C4—C5—C6—C1	−0.2 (5)	C15—C16—C17—C18	0.2 (4)
O1—P1—C7—C8	171.4 (2)	C14—N2—C18—C17	−0.6 (4)
C13—P1—C7—C8	45.2 (3)	C16—C17—C18—N2	0.6 (5)
C1—P1—C7—C8	−65.8 (3)	C14—N1—C19—C20	77.6 (3)
O1—P1—C7—C12	−11.0 (2)	C13—N1—C19—C20	−128.9 (2)
C13—P1—C7—C12	−137.2 (2)	N1—C19—C20—C25	19.6 (4)
C1—P1—C7—C12	111.8 (2)	N1—C19—C20—C21	−162.7 (2)
C12—C7—C8—C9	−1.8 (4)	C25—C20—C21—C22	0.8 (4)
P1—C7—C8—C9	175.8 (2)	C19—C20—C21—C22	−177.1 (3)
C7—C8—C9—C10	0.6 (5)	C20—C21—C22—C23	−0.7 (5)
C8—C9—C10—C11	1.0 (5)	C21—C22—C23—C24	−0.2 (5)
C9—C10—C11—C12	−1.4 (5)	C22—C23—C24—C25	1.1 (5)
C10—C11—C12—C7	0.2 (5)	C21—C20—C25—C24	0.1 (4)
C8—C7—C12—C11	1.4 (4)	C19—C20—C25—C24	177.8 (3)
P1—C7—C12—C11	−176.4 (2)	C23—C24—C25—C20	−1.0 (4)
C14—N1—C13—P1	−132.0 (2)

Experimental details

Crystal data
Chemical formula	C₂₅H₂₃N₂OP
M_r	398.42
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.256 (3), 14.834 (5), 15.957 (5)
β (°)	104.979 (6)
V (Å³)	2116.5 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.971, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	8613, 3727, 2051
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.120, 0.97
No. of reflections	3727
No. of parameters	262
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.26

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998) and SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top

P1—O1	1.4815 (18)	P1—C13	1.804 (2)
P1—C7	1.799 (3)	P1—C1	1.808 (3)

O1—P1—C7	111.44 (11)	O1—P1—C1	111.55 (12)
O1—P1—C13	114.16 (12)	C7—P1—C1	107.96 (12)
C7—P1—C13	108.12 (12)	C13—P1—C1	103.14 (12)

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{[N-Benzyl-N-(2-pyridyl)­amino]­methyl­ene}di­phenyl­phosphine oxide

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{[N-Benzyl-N-(2-pyridyl)amino]methylene}diphenylphosphine oxide