Crystal structure of tert-butyl­diphenyl­phosphine oxide

Agbeworvi, G.; Assefa, Z.; Sykora, R.E.; Taylor, J.D.

doi:10.1107/S2056989015008919

organic compounds

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Volume 71| Part 6| June 2015| Page o400

doi:10.1107/S2056989015008919

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Crystal structure of tert-butyldiphenylphosphine oxide

George Agbeworvi,^a Zerihun Assefa,^a ^* Richard E. Sykora ^b and Jared D. Taylor ^b

^a1601 E Market St., Department of Chemistry, North Carolina A & T State University, Greensboro, NC 27411, USA, and ^bUniversity of South Alabama, Department of Chemistry, Mobile, AL 36688-0002, USA
^*Correspondence e-mail: zassefa@ncat.edu

Edited by P. C. Healy, Griffith University, Australia (Received 18 April 2015; accepted 7 May 2015; online 13 May 2015)

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.

Keywords: crystal structure; phosphine oxide.

CCDC reference: 1063801

1. 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.

2. Experimental

2.1. Crystal data

C₁₆H₁₉OP
M_r = 258.28
Monoclinic, P 2₁
a = 6.3432 (6) Å
b = 9.5219 (9) Å
c = 12.4556 (15) Å
β = 101.665 (10)°
V = 736.78 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 293 K
0.4 × 0.15 × 0.04 mm

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 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)

Table 1
Selected bond lengths (Å)

P1—O1	1.4897 (14)
P1—C1	1.821 (3)
P1—C7	1.825 (3)
P1—C13	1.841 (3)

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 ).

Supporting information

CCDC reference: 1063801

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015008919/hg5439sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015008919/hg5439Isup2.hkl

checkCIF report

Synthesis and crystallization top

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).

Refinement top

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.

Related literature top

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

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014)); 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 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top

	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

tert-Butyldiphenylphosphine oxide top

Crystal data top

C₁₆H₁₉OP	F(000) = 276
M_r = 258.28	D_x = 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 top

Agilent Xcalibur, Eos diffractometer	2713 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2203 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 16.0514 pixels mm^-1	θ_max = 25.4°, θ_min = 2.7°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −11→11
T_min = 0.842, T_max = 1.000	l = −14→14
11029 measured 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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0343P)² + 0.0459P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2713 reflections	Δρ_max = 0.18 e Å⁻³
166 parameters	Δρ_min = −0.24 e Å⁻³
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: heavy-atom method	Absolute structure parameter: 0.19 (10)

Crystal data top

C₁₆H₁₉OP	V = 736.78 (13) Å³
M_r = 258.28	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.3432 (6) Å	µ = 0.17 mm⁻¹
b = 9.5219 (9) Å	T = 293 K
c = 12.4556 (15) Å	0.4 × 0.15 × 0.04 mm
β = 101.665 (10)°

Data collection top

Agilent Xcalibur, Eos diffractometer	2713 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	2203 reflections with I > 2σ(I)
T_min = 0.842, T_max = 1.000	R_int = 0.049
11029 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.086	Δρ_max = 0.18 e Å⁻³
S = 1.05	Δρ_min = −0.24 e Å⁻³
2713 reflections	Absolute structure: Flack (1983)
166 parameters	Absolute structure parameter: 0.19 (10)
1 restraint

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 > 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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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)

Selected bond lengths (Å) top

P1—O1	1.4897 (14)	P1—C7	1.825 (3)
P1—C1	1.821 (3)	P1—C13	1.841 (3)

Acknowledgements

The authors kindly acknowledge support from the National Science Foundation, CHE-0959406 (ZA) and CHE-0846680 (RES).

References

Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England. Google Scholar
Al-Farhan, K. A. (1992). J. Crystallogr. Spectrosc. Res. 22, 687–689. CSD CrossRef CAS Web of Science Google Scholar
Caddy, J., Coyanis, E. M., Lemmerer, A., Khanye, S. D. & Omondi, B. (2007). Acta Cryst. E63, o1032–o1033. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Orama, O. & Koskinen, J. T. (1994). Acta Cryst. C50, 608–609. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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