Crystal structure of tert-butyl­diphenyl­phosphine oxide

Abstract

In the structure of the title triorganophosphine oxide, C₁₆H₁₉OP, the P—O bond is 1.490 (1) Å. The P atom has a distorted tetrahedral geometry. The O atom inter­acts with both phenyl groups of a neighboring mol­ecule [C⋯O = 2.930 (3) and 2.928 (4) Å]. The C—O interaction directs an extended supramolecular arrangement along the a-axis.

Related literature  

For the structures of related phosphine oxides Ph₃P=O, EtPh₂P=O and BuPh₂P=O, see: Al-Farhan (1992 ▸), Orama & Koskinen (1994 ▸) and Caddy et al. (2007 ▸), respectively.

Experimental  

Crystal data  

• C₁₆H₁₉OP

• M _r = 258.28

• Monoclinic,

• a = 6.3432 (6) Å

• b = 9.5219 (9) Å

• c = 12.4556 (15) Å

• β = 101.665 (10)°

• V = 736.78 (13) ų

• Z = 2

• Mo Kα radiation

• μ = 0.17 mm⁻¹

• T = 293 K

• 0.4 × 0.15 × 0.04 mm

Data collection  

• Agilent Xcalibur, Eos diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ▸) T _min = 0.842, T _max = 1.000

• 11029 measured reflections

• 2713 independent reflections

• 2203 reflections with I > 2σ(I)

• R _int = 0.049

Refinement  

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.086

• S = 1.05

• 2713 reflections

• 166 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

• Absolute structure: Flack (1983 ▸)

• Absolute structure parameter: 0.19 (10)

Data collection: CrysAlis PRO (Agilent, 2014 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2 and publCIF (Westrip, 2010 ▸).

Supplementary Material

CCDC reference: 1063801

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths ().

P1O1	1.4897(14)
P1C1	1.821(3)
P1C7	1.825(3)
P1C13	1.841(3)

supplementary crystallographic information

S1. Synthesis and crystallization

The tert-butyl­diphenyl­phosphine oxide was unintentionally obtained during the reaction used to coordinate the unoxidized ligand to gold(I). The product was obtained after mixing tert-butyl­diphenyl­phosphine (0.0600 g, 0.24 mmol) with a solution of (C₄H₈S)AuCl (0.0264 g, 0.08 mmol) in tetra­hydro­furan (20 mL) at -80^oC. The reaction solution was stirred for 3 hours and the solvent removed totally by purging nitro­gen gas into the solution. The residue was then recrystallized from CH₂Cl₂/n-hexane mixture within six days. Partial evaporation of the solvent provided quality crystals of the title compound. Yield 90%. Melting point 137^oC (decomposition). ¹H NMR (CD₂Cl₂) [δ (ppm)]: 1.3(s),7.3(m), 7.6(m), 7.9(m). For ³¹P NMR in CD₂Cl₂ [δ (ppm)]: 38.96. Infrared data (cm^-1): 3032 (C–H, Ar), 2908 (C–H, CH₃), 1597 (C=C, Ar), 1165 (P=O), 1126 (P–Ar).

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H-atoms were placed in calculated positions and allowed to ride during subsequent refinement, with U_iso(H) = 1.2U_eq(C) and C—H distances of 0.93 Å for ring hydrogens and with U_iso(H) = 1.5U_eq(O) and C—H distances of 0.96 Å for methyl hydrogens.

Figures

Fig. 1.

A ball-and-stick representation of the molecular structure of I.

Fig. 2.

Molecular packing with short C—H···O contacts indicated by dashed lines

Crystal data

C16H19OP	F(000) = 276
Mr = 258.28	Dx = 1.164 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 6.3432 (6) Å	Cell parameters from 2279 reflections
b = 9.5219 (9) Å	θ = 3.3–23.1°
c = 12.4556 (15) Å	µ = 0.17 mm−1
β = 101.665 (10)°	T = 293 K
V = 736.78 (13) Å3	Plate, colourless
Z = 2	0.4 × 0.15 × 0.04 mm

Data collection

Agilent Xcalibur, Eos diffractometer	2713 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2203 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 16.0514 pixels mm-1	θmax = 25.4°, θmin = 2.7°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −11→11
Tmin = 0.842, Tmax = 1.000	l = −14→14
11029 measured reflections

Refinement

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)] = 0.044	H-atom parameters constrained
wR(F2) = 0.086	w = 1/[σ2(Fo2) + (0.0343P)2 + 0.0459P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2713 reflections	Δρmax = 0.18 e Å−3
166 parameters	Δρmin = −0.24 e Å−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: heavy-atom method	Absolute structure parameter: 0.19 (10)

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 > 2σ(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
P1	0.87488 (9)	0.74951 (7)	0.71978 (5)	0.03371 (18)
O1	1.1119 (2)	0.7455 (2)	0.72615 (15)	0.0475 (5)
C2	0.5797 (4)	0.5351 (3)	0.7611 (2)	0.0437 (7)
H2	0.4792	0.6045	0.7664	0.052*
C1	0.7771 (4)	0.5727 (3)	0.7363 (2)	0.0349 (7)
C14	0.7903 (5)	0.7211 (4)	0.4984 (2)	0.0631 (10)
H14A	0.9440	0.7152	0.5077	0.095*
H14B	0.7310	0.7586	0.4271	0.095*
H14C	0.7323	0.6291	0.5050	0.095*
C6	0.9206 (5)	0.4655 (3)	0.7265 (2)	0.0485 (8)
H6	1.0527	0.4876	0.7093	0.058*
C4	0.6771 (5)	0.2920 (3)	0.7685 (3)	0.0565 (9)
H4	0.6443	0.1988	0.7802	0.068*
C3	0.5318 (5)	0.3973 (3)	0.7776 (2)	0.0499 (8)
H3	0.4003	0.3745	0.7951	0.060*
C7	0.8146 (4)	0.8617 (3)	0.8285 (2)	0.0375 (7)
C8	0.6180 (4)	0.8754 (3)	0.8609 (3)	0.0513 (8)
H8	0.4985	0.8257	0.8246	0.062*
C10	0.7712 (5)	1.0408 (4)	1.0008 (2)	0.0609 (9)
H10	0.7562	1.0998	1.0583	0.073*
C9	0.6004 (5)	0.9632 (4)	0.9473 (3)	0.0615 (10)
H9	0.4692	0.9697	0.9694	0.074*
C12	0.9867 (4)	0.9407 (3)	0.8838 (3)	0.0543 (9)
H12	1.1197	0.9334	0.8637	0.065*
C11	0.9640 (5)	1.0303 (4)	0.9686 (3)	0.0671 (10)
H11	1.0807	1.0836	1.0036	0.081*
C5	0.8706 (5)	0.3264 (3)	0.7418 (3)	0.0590 (9)
H5	0.9682	0.2560	0.7341	0.071*
C13	0.7324 (4)	0.8175 (3)	0.5864 (2)	0.0361 (6)
C16	0.8231 (5)	0.9656 (3)	0.5733 (3)	0.0646 (10)
H16A	0.7806	1.0281	0.6255	0.097*
H16B	0.7678	0.9994	0.5004	0.097*
H16C	0.9774	0.9613	0.5858	0.097*
C15	0.4891 (4)	0.8239 (4)	0.5752 (3)	0.0577 (9)
H15A	0.4356	0.7323	0.5876	0.087*
H15B	0.4240	0.8552	0.5028	0.087*
H15C	0.4543	0.8885	0.6283	0.087*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
P1	0.0276 (3)	0.0354 (4)	0.0388 (4)	−0.0001 (4)	0.0084 (3)	0.0003 (4)
O1	0.0296 (8)	0.0516 (11)	0.0634 (12)	0.0015 (12)	0.0142 (8)	−0.0006 (14)
C2	0.0414 (16)	0.0407 (17)	0.0509 (19)	0.0010 (14)	0.0138 (13)	0.0036 (15)
C1	0.0355 (15)	0.0370 (17)	0.0306 (16)	0.0023 (12)	0.0031 (12)	0.0032 (12)
C14	0.081 (2)	0.068 (3)	0.0415 (18)	0.0185 (19)	0.0145 (16)	−0.0007 (17)
C6	0.0436 (17)	0.0429 (19)	0.060 (2)	0.0050 (13)	0.0127 (16)	0.0019 (15)
C4	0.070 (2)	0.036 (2)	0.059 (2)	−0.0047 (15)	0.0044 (17)	0.0081 (14)
C3	0.0496 (18)	0.047 (2)	0.054 (2)	−0.0094 (15)	0.0141 (15)	0.0064 (15)
C7	0.0312 (14)	0.0432 (17)	0.0368 (17)	−0.0002 (13)	0.0036 (12)	−0.0016 (13)
C8	0.0411 (17)	0.067 (2)	0.0468 (19)	−0.0115 (15)	0.0110 (14)	−0.0145 (16)
C10	0.063 (2)	0.078 (2)	0.0397 (19)	0.005 (2)	0.0079 (16)	−0.0177 (19)
C9	0.050 (2)	0.086 (3)	0.052 (2)	−0.0016 (18)	0.0181 (17)	−0.0197 (19)
C12	0.0380 (17)	0.071 (2)	0.052 (2)	−0.0032 (16)	0.0048 (15)	−0.0153 (18)
C11	0.055 (2)	0.081 (3)	0.061 (2)	−0.010 (2)	0.0004 (18)	−0.028 (2)
C5	0.060 (2)	0.0360 (19)	0.081 (3)	0.0131 (16)	0.0143 (18)	−0.0008 (17)
C13	0.0351 (14)	0.0347 (16)	0.0405 (17)	0.0010 (12)	0.0128 (12)	0.0037 (13)
C16	0.078 (2)	0.041 (2)	0.073 (3)	−0.0094 (17)	0.0122 (19)	0.0163 (17)
C15	0.0439 (16)	0.075 (2)	0.051 (2)	0.0054 (16)	0.0026 (15)	0.0143 (18)

Geometric parameters (Å, º)

P1—O1	1.4897 (14)	C7—C12	1.388 (3)
P1—C1	1.821 (3)	C8—H8	0.9300
P1—C7	1.825 (3)	C8—C9	1.385 (4)
P1—C13	1.841 (3)	C10—H10	0.9300
C2—H2	0.9300	C10—C9	1.368 (4)
C2—C1	1.395 (3)	C10—C11	1.366 (4)
C2—C3	1.372 (4)	C9—H9	0.9300
C1—C6	1.390 (3)	C12—H12	0.9300
C14—H14A	0.9600	C12—C11	1.388 (4)
C14—H14B	0.9600	C11—H11	0.9300
C14—H14C	0.9600	C5—H5	0.9300
C14—C13	1.530 (4)	C13—C16	1.544 (4)
C6—H6	0.9300	C13—C15	1.523 (3)
C6—C5	1.384 (4)	C16—H16A	0.9600
C4—H4	0.9300	C16—H16B	0.9600
C4—C3	1.382 (4)	C16—H16C	0.9600
C4—C5	1.374 (4)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C7—C8	1.393 (3)	C15—H15C	0.9600
O1—P1—C1	109.48 (12)	C9—C10—H10	120.5
O1—P1—C7	109.63 (12)	C11—C10—H10	120.5
O1—P1—C13	111.29 (10)	C11—C10—C9	119.0 (3)
C1—P1—C7	109.29 (12)	C8—C9—H9	119.2
C1—P1—C13	108.10 (12)	C10—C9—C8	121.6 (3)
C7—P1—C13	109.02 (12)	C10—C9—H9	119.2
C1—C2—H2	119.5	C7—C12—H12	119.4
C3—C2—H2	119.5	C11—C12—C7	121.2 (3)
C3—C2—C1	120.9 (3)	C11—C12—H12	119.4
C2—C1—P1	127.1 (2)	C10—C11—C12	120.4 (3)
C6—C1—P1	115.15 (19)	C10—C11—H11	119.8
C6—C1—C2	117.7 (3)	C12—C11—H11	119.8
H14A—C14—H14B	109.5	C6—C5—H5	119.9
H14A—C14—H14C	109.5	C4—C5—C6	120.1 (3)
H14B—C14—H14C	109.5	C4—C5—H5	119.9
C13—C14—H14A	109.5	C14—C13—P1	106.90 (19)
C13—C14—H14B	109.5	C14—C13—C16	108.9 (2)
C13—C14—H14C	109.5	C16—C13—P1	106.9 (2)
C1—C6—H6	119.4	C15—C13—P1	113.58 (18)
C5—C6—C1	121.2 (3)	C15—C13—C14	110.2 (2)
C5—C6—H6	119.4	C15—C13—C16	110.2 (2)
C3—C4—H4	120.3	C13—C16—H16A	109.5
C5—C4—H4	120.3	C13—C16—H16B	109.5
C5—C4—C3	119.3 (3)	C13—C16—H16C	109.5
C2—C3—C4	120.7 (3)	H16A—C16—H16B	109.5
C2—C3—H3	119.7	H16A—C16—H16C	109.5
C4—C3—H3	119.7	H16B—C16—H16C	109.5
C8—C7—P1	127.2 (2)	C13—C15—H15A	109.5
C12—C7—P1	115.06 (19)	C13—C15—H15B	109.5
C12—C7—C8	117.8 (3)	C13—C15—H15C	109.5
C7—C8—H8	120.0	H15A—C15—H15B	109.5
C9—C8—C7	120.0 (3)	H15A—C15—H15C	109.5
C9—C8—H8	120.0	H15B—C15—H15C	109.5
P1—C1—C6—C5	177.2 (3)	C3—C2—C1—C6	1.5 (4)
P1—C7—C8—C9	178.4 (3)	C3—C4—C5—C6	1.3 (5)
P1—C7—C12—C11	−179.9 (3)	C7—P1—C1—C2	43.6 (3)
O1—P1—C1—C2	163.7 (2)	C7—P1—C1—C6	−134.0 (2)
O1—P1—C1—C6	−14.0 (2)	C7—P1—C13—C14	179.33 (18)
O1—P1—C7—C8	−169.2 (3)	C7—P1—C13—C16	62.9 (2)
O1—P1—C7—C12	10.6 (3)	C7—P1—C13—C15	−58.9 (2)
O1—P1—C13—C14	58.3 (2)	C7—C8—C9—C10	1.7 (5)
O1—P1—C13—C16	−58.2 (2)	C7—C12—C11—C10	1.2 (5)
O1—P1—C13—C15	−180.0 (2)	C8—C7—C12—C11	0.0 (5)
C2—C1—C6—C5	−0.6 (4)	C9—C10—C11—C12	−1.0 (5)
C1—P1—C7—C8	−49.2 (3)	C12—C7—C8—C9	−1.4 (4)
C1—P1—C7—C12	130.6 (2)	C11—C10—C9—C8	−0.5 (5)
C1—P1—C13—C14	−62.0 (2)	C5—C4—C3—C2	−0.4 (5)
C1—P1—C13—C16	−178.44 (19)	C13—P1—C1—C2	−75.0 (2)
C1—P1—C13—C15	59.8 (2)	C13—P1—C1—C6	107.4 (2)
C1—C2—C3—C4	−1.0 (4)	C13—P1—C7—C8	68.7 (3)
C1—C6—C5—C4	−0.7 (5)	C13—P1—C7—C12	−111.4 (2)
C3—C2—C1—P1	−176.1 (2)