4-(Di­phenyl­phosphinoyl)-3-methyl-N-phenyl-1,2-isoxazole-5-carbox­amide

The title compound, C₂₃H₁₉N₂O₃P, was prepared by the reaction of ethynyldi­phenyl­phosphine oxide with phenyl isocyanate, triethyl­amine and nitoethane in benzene. The molecular structure is stabilized by an intramolecular N-H...O hydrogen bond.

S1. Comment

Ethynyldiphenylphosphine oxide (Charrier et al., 1966) was treated by the method of Mukaiyama & Hoshino (1960) with phenyl isocyanate, triethylamine and nitroethane in benzene to give 4-(diphenylphosphinoyl)-3-methylisoxazole and 5-(diphenylphosphinoyl)-3-methylisoxazole in a 1:1 ratio. The title compound, (I), was formed as a by-product in 16% yield.

S2. Experimental

The title compound was obtained in 16% yield from the reaction of ethynyldiphenylphosphine oxide with phenyl isocyanate, triethylamine and nitroethane in benzene (Charrier et al., 1966; Mukaiyama & Hoshino, 1960). The solvent was removed and the residue chromatographed on a silica-gel column with ethyl acetate as eluent. Colourless crystals were grown by slow evaporation from the ethyl acetate solution at room temperature, m.p. 467–468 K.

S3. Refinement

Crystal decay was monitored by repeating the initial frames at the end of data collection. Analysing the duplicate reflections there were no indications for any decay. H atoms were placed geometrically and refined with a riding model (including free rotation about C—C) with U_iso constrained to be 1.5U_eq of the carrier atom.

Computing details

Data collection: Nonius KappaCCD software; cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PARST95 (Nardelli, 1995).

(I)

Crystal data

C23H19N2O3P	Z = 2
Mr = 402.37	F(000) = 420
Triclinic, P1	Dx = 1.328 Mg m^−3
a = 7.4055 (2) Å	Mo Kα radiation, λ = 0.71069 Å
b = 10.3008 (4) Å	Cell parameters from 11324 reflections
c = 13.6543 (5) Å	θ = 3.4–25.0°
α = 79.896 (1)°	µ = 0.16 mm^−1
β = 79.283 (2)°	T = 291 K
γ = 85.338 (2)°	Block, colourless
V = 1006.27 (6) Å^3	0.30 × 0.20 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer	2477 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 25.0°, θmin = 3.4°
Detector resolution: 10 vertical, 18 horizontal pixels mm^-1	h = −7→7
360 frames via ω–rotation (Δω = 1°) at different θ values and two times 20 s per frame scans	k = −12→12
11324 measured reflections	l = −15→16
3308 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.00	Calculated w = 1/[σ^2(Fo^2) + (0.0617P)^2] where P = (Fo^2 + 2Fc^2)/3
3308 reflections	(Δ/σ)max < 0.001
263 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. The data collection covered the whole sphere of the reciprocal space. The crystal to detector distance was 3.0 cm with a detector offset of 5°.

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.

The structure was solved by direct methods (Sheldrick, 1990) and successive difference Fourier syntheses. Refinement applied full-matrix least-squares methods (Sheldrick, 1997).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	0.39934 (6)	0.86003 (4)	0.79232 (3)	0.04088 (16)
O1	0.57658 (15)	1.11888 (12)	0.54818 (9)	0.0518 (3)
O2	0.24260 (15)	0.93150 (12)	0.84930 (9)	0.0523 (3)
O3	0.26237 (17)	1.24690 (13)	0.55543 (10)	0.0639 (4)
N1	0.14088 (18)	1.13211 (14)	0.70841 (11)	0.0488 (4)
H6	0.1641	1.0663	0.7533	0.073*
N2	0.73838 (18)	1.03827 (15)	0.55140 (12)	0.0549 (4)
C1	0.2730 (2)	1.15941 (17)	0.62718 (14)	0.0460 (4)
C2	0.8536 (2)	0.8487 (2)	0.65513 (16)	0.0651 (6)
H4A	0.9606	0.8638	0.6036	0.098*
H4B	0.8130	0.7618	0.6578	0.098*
H4C	0.8835	0.8563	0.7193	0.098*
C3	0.7040 (2)	0.94870 (18)	0.63144 (14)	0.0457 (4)
C4	0.5181 (2)	0.96539 (16)	0.68440 (12)	0.0398 (4)
C5	0.4488 (2)	1.07401 (16)	0.62770 (12)	0.0406 (4)
C11	0.3263 (2)	0.72537 (16)	0.74497 (12)	0.0397 (4)
C12	0.1723 (2)	0.65971 (19)	0.80026 (15)	0.0549 (5)
H12	0.1140	0.6841	0.8613	0.082*
C13	0.1064 (3)	0.5588 (2)	0.76444 (19)	0.0695 (6)
H13	0.0044	0.5149	0.8016	0.104*
C14	0.1916 (3)	0.5231 (2)	0.6739 (2)	0.0719 (6)
H14	0.1465	0.4554	0.6497	0.108*
C15	0.3419 (3)	0.5866 (2)	0.61951 (17)	0.0672 (6)
H15	0.3988	0.5619	0.5584	0.101*
C16	0.4107 (2)	0.68731 (18)	0.65433 (14)	0.0515 (5)
H16	0.5137	0.7296	0.6168	0.077*
C21	0.5644 (2)	0.79572 (17)	0.87200 (12)	0.0421 (4)
C22	0.6064 (2)	0.66234 (18)	0.89799 (14)	0.0510 (5)
H22	0.5601	0.6016	0.8673	0.077*
C23	0.7175 (3)	0.6190 (2)	0.96973 (15)	0.0623 (5)
H23	0.7438	0.5291	0.9880	0.093*
C24	0.7885 (3)	0.7086 (2)	1.01374 (15)	0.0664 (6)
H24	0.8630	0.6791	1.0618	0.100*
C25	0.7508 (3)	0.8408 (2)	0.98772 (16)	0.0694 (6)
H25	0.8009	0.9009	1.0173	0.104*
C26	0.6380 (3)	0.8853 (2)	0.91719 (15)	0.0596 (5)
H26	0.6113	0.9753	0.9000	0.089*
C31	−0.0327 (2)	1.19999 (16)	0.72818 (14)	0.0453 (4)
C32	−0.1179 (2)	1.19170 (19)	0.82779 (15)	0.0550 (5)
H32	−0.0613	1.1425	0.8786	0.083*
C33	−0.2882 (3)	1.2567 (2)	0.85243 (17)	0.0657 (6)
H33	−0.3446	1.2510	0.9197	0.099*
C34	−0.3730 (3)	1.3287 (2)	0.77833 (19)	0.0706 (6)
H34	−0.4867	1.3724	0.7947	0.106*
C35	−0.2884 (3)	1.3357 (2)	0.67964 (18)	0.0736 (6)
H35	−0.3462	1.3846	0.6292	0.110*
C36	−0.1199 (3)	1.2724 (2)	0.65308 (16)	0.0611 (5)
H36	−0.0652	1.2780	0.5855	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0441 (3)	0.0398 (3)	0.0364 (3)	−0.00124 (18)	−0.00301 (18)	−0.0048 (2)
O1	0.0493 (7)	0.0479 (7)	0.0507 (8)	−0.0017 (5)	−0.0005 (6)	0.0028 (6)
O2	0.0542 (7)	0.0507 (7)	0.0456 (7)	0.0054 (6)	0.0040 (6)	−0.0081 (6)
O3	0.0691 (9)	0.0540 (8)	0.0567 (9)	0.0113 (6)	−0.0015 (7)	0.0065 (7)
N1	0.0453 (8)	0.0489 (9)	0.0468 (9)	0.0059 (6)	−0.0035 (7)	−0.0015 (7)
N2	0.0434 (8)	0.0577 (10)	0.0571 (10)	−0.0004 (7)	−0.0006 (7)	−0.0014 (9)
C1	0.0529 (10)	0.0384 (10)	0.0465 (11)	0.0001 (8)	−0.0084 (8)	−0.0073 (9)
C2	0.0449 (11)	0.0782 (14)	0.0635 (13)	0.0097 (9)	−0.0025 (9)	−0.0017 (11)
C3	0.0421 (9)	0.0485 (11)	0.0439 (11)	−0.0030 (8)	−0.0037 (7)	−0.0045 (9)
C4	0.0406 (9)	0.0402 (10)	0.0383 (10)	−0.0027 (7)	−0.0038 (7)	−0.0085 (8)
C5	0.0431 (9)	0.0391 (10)	0.0382 (10)	−0.0059 (7)	−0.0025 (7)	−0.0054 (8)
C11	0.0397 (9)	0.0391 (9)	0.0385 (10)	−0.0011 (7)	−0.0083 (7)	−0.0006 (8)
C12	0.0479 (10)	0.0556 (12)	0.0582 (13)	−0.0063 (9)	−0.0051 (9)	−0.0037 (10)
C13	0.0573 (12)	0.0531 (13)	0.0966 (18)	−0.0138 (10)	−0.0177 (12)	0.0011 (12)
C14	0.0819 (15)	0.0477 (12)	0.0965 (19)	−0.0023 (11)	−0.0381 (14)	−0.0166 (13)
C15	0.0890 (16)	0.0535 (13)	0.0647 (14)	0.0053 (11)	−0.0212 (12)	−0.0207 (11)
C16	0.0604 (11)	0.0462 (11)	0.0464 (11)	−0.0016 (8)	−0.0067 (9)	−0.0071 (9)
C21	0.0469 (9)	0.0441 (10)	0.0331 (9)	−0.0043 (7)	−0.0020 (7)	−0.0048 (8)
C22	0.0537 (11)	0.0485 (11)	0.0504 (12)	−0.0035 (8)	−0.0104 (8)	−0.0052 (9)
C23	0.0624 (12)	0.0585 (13)	0.0613 (13)	0.0017 (9)	−0.0154 (10)	0.0057 (10)
C24	0.0603 (12)	0.0871 (17)	0.0511 (13)	−0.0028 (11)	−0.0196 (10)	0.0004 (12)
C25	0.0741 (14)	0.0792 (17)	0.0636 (14)	−0.0088 (11)	−0.0271 (11)	−0.0165 (12)
C26	0.0688 (13)	0.0546 (12)	0.0591 (13)	−0.0060 (9)	−0.0181 (10)	−0.0111 (10)
C31	0.0441 (10)	0.0405 (10)	0.0530 (12)	−0.0022 (7)	−0.0098 (8)	−0.0105 (9)
C32	0.0496 (11)	0.0589 (12)	0.0545 (13)	−0.0032 (9)	−0.0062 (9)	−0.0067 (10)
C33	0.0546 (12)	0.0761 (15)	0.0638 (14)	−0.0011 (10)	0.0032 (10)	−0.0199 (12)
C34	0.0548 (12)	0.0718 (14)	0.0849 (18)	0.0122 (10)	−0.0093 (11)	−0.0222 (13)
C35	0.0599 (13)	0.0846 (16)	0.0764 (17)	0.0224 (11)	−0.0218 (11)	−0.0152 (13)
C36	0.0589 (12)	0.0710 (14)	0.0553 (13)	0.0091 (9)	−0.0149 (9)	−0.0156 (11)

Geometric parameters (Å, º)

P1—O2	1.4903 (11)	C15—C16	1.382 (3)
P1—C11	1.7891 (17)	C15—H15	0.9300
P1—C21	1.7962 (17)	C16—H16	0.9300
P1—C4	1.7986 (17)	C21—C22	1.382 (2)
O1—C5	1.3420 (19)	C21—C26	1.391 (2)
O1—N2	1.4043 (17)	C22—C23	1.386 (2)
O3—C1	1.219 (2)	C22—H22	0.9300
N1—C1	1.341 (2)	C23—C24	1.372 (3)
N1—C31	1.416 (2)	C23—H23	0.9300
N1—H6	0.8600	C24—C25	1.365 (3)
N2—C3	1.301 (2)	C24—H24	0.9300
C1—C5	1.511 (2)	C25—C26	1.385 (3)
C2—C3	1.491 (2)	C25—H25	0.9300
C2—H4A	0.9600	C26—H26	0.9300
C2—H4B	0.9600	C31—C32	1.380 (2)
C2—H4C	0.9600	C31—C36	1.387 (2)
C3—C4	1.443 (2)	C32—C33	1.391 (2)
C4—C5	1.366 (2)	C32—H32	0.9300
C11—C16	1.385 (2)	C33—C34	1.366 (3)
C11—C12	1.398 (2)	C33—H33	0.9300
C12—C13	1.381 (3)	C34—C35	1.369 (3)
C12—H12	0.9300	C34—H34	0.9300
C13—C14	1.376 (3)	C35—C36	1.377 (3)
C13—H13	0.9300	C35—H35	0.9300
C14—C15	1.364 (3)	C36—H36	0.9300
C14—H14	0.9300
O2—P1—C11	112.25 (7)	C14—C15—H15	119.7
O2—P1—C21	110.38 (7)	C16—C15—H15	119.7
C11—P1—C21	108.13 (7)	C15—C16—C11	120.13 (18)
O2—P1—C4	112.25 (7)	C15—C16—H16	119.9
C11—P1—C4	106.19 (8)	C11—C16—H16	119.9
C21—P1—C4	107.39 (7)	C22—C21—C26	119.13 (16)
C5—O1—N2	108.92 (12)	C22—C21—P1	123.30 (13)
C1—N1—C31	126.99 (15)	C26—C21—P1	117.23 (13)
C1—N1—H6	116.5	C21—C22—C23	120.09 (17)
C31—N1—H6	116.5	C21—C22—H22	120.0
C3—N2—O1	106.27 (13)	C23—C22—H22	120.0
O3—C1—N1	125.43 (16)	C24—C23—C22	120.02 (19)
O3—C1—C5	118.75 (16)	C24—C23—H23	120.0
N1—C1—C5	115.82 (15)	C22—C23—H23	120.0
C3—C2—H4A	109.5	C25—C24—C23	120.63 (19)
C3—C2—H4B	109.5	C25—C24—H24	119.7
H4A—C2—H4B	109.5	C23—C24—H24	119.7
C3—C2—H4C	109.5	C24—C25—C26	119.95 (19)
H4A—C2—H4C	109.5	C24—C25—H25	120.0
H4B—C2—H4C	109.5	C26—C25—H25	120.0
N2—C3—C4	111.36 (15)	C25—C26—C21	120.18 (19)
N2—C3—C2	118.32 (15)	C25—C26—H26	119.9
C4—C3—C2	130.32 (16)	C21—C26—H26	119.9
C5—C4—C3	103.33 (14)	C32—C31—C36	119.22 (17)
C5—C4—P1	128.10 (13)	C32—C31—N1	117.35 (16)
C3—C4—P1	128.34 (13)	C36—C31—N1	123.43 (17)
O1—C5—C4	110.11 (14)	C31—C32—C33	120.25 (18)
O1—C5—C1	110.36 (14)	C31—C32—H32	119.9
C4—C5—C1	139.53 (16)	C33—C32—H32	119.9
C16—C11—C12	118.85 (17)	C34—C33—C32	120.4 (2)
C16—C11—P1	122.96 (13)	C34—C33—H33	119.8
C12—C11—P1	118.13 (13)	C32—C33—H33	119.8
C13—C12—C11	120.12 (19)	C33—C34—C35	119.07 (19)
C13—C12—H12	119.9	C33—C34—H34	120.5
C11—C12—H12	119.9	C35—C34—H34	120.5
C14—C13—C12	120.1 (2)	C34—C35—C36	121.8 (2)
C14—C13—H13	120.0	C34—C35—H35	119.1
C12—C13—H13	120.0	C36—C35—H35	119.1
C15—C14—C13	120.1 (2)	C35—C36—C31	119.30 (19)
C15—C14—H14	119.9	C35—C36—H36	120.4
C13—C14—H14	119.9	C31—C36—H36	120.4
C14—C15—C16	120.7 (2)
C5—O1—N2—C3	−0.03 (18)	P1—C11—C12—C13	177.32 (14)
C31—N1—C1—O3	−1.6 (3)	C11—C12—C13—C14	−0.4 (3)
C31—N1—C1—C5	177.49 (14)	C12—C13—C14—C15	0.4 (3)
O1—N2—C3—C4	0.34 (19)	C13—C14—C15—C16	0.0 (3)
O1—N2—C3—C2	−179.37 (15)	C14—C15—C16—C11	−0.4 (3)
N2—C3—C4—C5	−0.5 (2)	C12—C11—C16—C15	0.4 (3)
C2—C3—C4—C5	179.15 (18)	P1—C11—C16—C15	−176.79 (13)
N2—C3—C4—P1	174.40 (13)	O2—P1—C21—C22	116.80 (15)
C2—C3—C4—P1	−5.9 (3)	C11—P1—C21—C22	−6.34 (17)
O2—P1—C4—C5	−28.55 (18)	C4—P1—C21—C22	−120.54 (15)
C11—P1—C4—C5	94.47 (16)	O2—P1—C21—C26	−56.50 (15)
C21—P1—C4—C5	−150.04 (15)	C11—P1—C21—C26	−179.64 (13)
O2—P1—C4—C3	157.75 (14)	C4—P1—C21—C26	66.16 (15)
C11—P1—C4—C3	−79.24 (16)	C26—C21—C22—C23	1.3 (3)
C21—P1—C4—C3	36.25 (17)	P1—C21—C22—C23	−171.87 (13)
N2—O1—C5—C4	−0.31 (18)	C21—C22—C23—C24	−1.1 (3)
N2—O1—C5—C1	179.47 (12)	C22—C23—C24—C25	0.1 (3)
C3—C4—C5—O1	0.48 (18)	C23—C24—C25—C26	0.8 (3)
P1—C4—C5—O1	−174.45 (12)	C24—C25—C26—C21	−0.7 (3)
C3—C4—C5—C1	−179.19 (19)	C22—C21—C26—C25	−0.4 (3)
P1—C4—C5—C1	5.9 (3)	P1—C21—C26—C25	173.18 (15)
O3—C1—C5—O1	5.5 (2)	C1—N1—C31—C32	−155.90 (17)
N1—C1—C5—O1	−173.71 (14)	C1—N1—C31—C36	24.6 (3)
O3—C1—C5—C4	−174.9 (2)	C36—C31—C32—C33	−0.8 (3)
N1—C1—C5—C4	6.0 (3)	N1—C31—C32—C33	179.64 (16)
O2—P1—C11—C16	146.24 (14)	C31—C32—C33—C34	0.3 (3)
C21—P1—C11—C16	−91.76 (15)	C32—C33—C34—C35	0.2 (3)
C4—P1—C11—C16	23.23 (16)	C33—C34—C35—C36	−0.1 (4)
O2—P1—C11—C12	−30.95 (15)	C34—C35—C36—C31	−0.4 (3)
C21—P1—C11—C12	91.05 (14)	C32—C31—C36—C35	0.8 (3)
C4—P1—C11—C12	−153.96 (13)	N1—C31—C36—C35	−179.64 (17)
C16—C11—C12—C13	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H6···O2	0.86	1.87	2.726 (2)	172