(3S)-4-Phenyl-3-(phenyl­amino­oxy)butan-2-one

The title compound, C₁₆H₁₇NO₂, is an inter­mediate in our work on chiral acyl­oins. The crystal structure shows that mol­ecules are linked by N—H...·O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.055
• wR factor = 0.145
• Data-to-parameter ratio = 8.8

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.751     1.000
            Tmin(prime) and Tmax expected:      0.963     0.993
            RR(prime) =      0.775
            Please check that your absorption correction is appropriate.
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.148
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.15
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.77
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C5     -   C6      ..       5.97 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.50
           From the CIF: _reflns_number_total               1571
           Count of symmetry unique reflns         1572
           Completeness (_total/calc)             99.94%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1     = .          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Chiral α-hydroxy ketones (acyloins) are useful synthetic intermediates (Davis & Chen, 1992). In recent years, three groups have reported proline and proline analogue-catalyzed α-aminoxylation of ketones (Córdova et al., 2004; Hayashi et al., 2004; Momiyama et al., 2004), those compounds can be converted to acyloins. In our work of chiral acyloins, we obtain the title compound (I), and here report its crystal structure. In the crystal packing of (I), the carbonyl O atom is engaged in H-bonding with the N—H of the adjacent molecule.

Related literature

For related literature, see: Córdova et al. (2004); Davis & Chen (1992); Farrugia (1997); Hayashi et al. (2004); Momiyama et al. (2004).

S2. Experimental

The 4-phenyl-butan-2-one (10 mmol) was added to a mixture of nitrosobenzene (1 mmol) and trans-4-tert-butyldimethylsiloxy-D-proline (30 mol %) in DMSO (4 ml). The reaction was quenched after 3 h of vigorous stirring at room temperature by addition of aqueous NH₄Cl solution. After work up, the residue was purified by silica gel chromatography. Colorless crystals were obtained by slow evaporation in petroleum and ethyl acetate at room temperature.

S3. Refinement

The hydrogen atoms were generated geometrically (C—H = 0.93, 0.98, 0.97 or 0.96Å for phenyl, tertiary, methylene or methyl H atoms respectively, and N—H = 0.86 Å) were included in the refinement in the riding model approximation except the NH where all parameters were refined. The displacement parameters of methyl H atoms were set to 1.5 times U_eq of the equivalent isotropic displacement parameters of their parent atoms, while those of other CH atoms were set to 1.2 times. In the absence of significant anomalous scattering effects, Friedel pairs were merged. The absolute configuration was assumed from the synthesis.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. ORTEPIII (Farrugia, 1997) plot of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms are drawn as spheres of arbitrary radii.

(3S)-4-phenyl-3-(phenylaminooxy)butan-2-one

Crystal data

C16H17NO2	F(000) = 544
Mr = 255.31	Dx = 1.184 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 756 reflections
a = 5.5950 (17) Å	θ = 5.0–47.7°
b = 15.847 (5) Å	µ = 0.08 mm^−1
c = 16.156 (5) Å	T = 293 K
V = 1432.4 (7) Å^3	Block, colourless
Z = 4	0.48 × 0.18 × 0.09 mm

Data collection

Bruker APEX area-detector diffractometer	1571 independent reflections
Radiation source: fine-focus sealed tube	781 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.148
φ scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −6→6
Tmin = 0.751, Tmax = 1.000	k = −19→17
7191 measured reflections	l = −19→16

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 0.85	w = 1/[σ^2(Fo^2) + (0.0647P)^2] where P = (Fo^2 + 2Fc^2)/3
1571 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.16 e Å^−3
1 restraint	Δρmin = −0.21 e Å^−3

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.5061 (6)	0.4253 (2)	0.66177 (17)	0.0762 (10)
O2	0.0167 (5)	0.42246 (18)	0.52562 (16)	0.0597 (8)
N1	−0.0743 (7)	0.4977 (3)	0.5659 (2)	0.0633 (11)
C1	0.2625 (7)	0.4174 (3)	0.5431 (2)	0.0510 (11)
H1	0.3403	0.4699	0.5255	0.061*
C2	0.3146 (9)	0.4024 (3)	0.6342 (3)	0.0613 (12)
C3	0.1367 (10)	0.3571 (3)	0.6863 (3)	0.0830 (15)
H3A	0.0567	0.3153	0.6535	0.124*
H3B	0.0217	0.3966	0.7073	0.124*
H3C	0.2170	0.3302	0.7317	0.124*
C4	0.3649 (9)	0.3440 (3)	0.4935 (2)	0.0645 (13)
H4A	0.5313	0.3365	0.5086	0.077*
H4B	0.2801	0.2929	0.5085	0.077*
C5	0.3484 (8)	0.3561 (3)	0.4006 (3)	0.0536 (11)
C6	0.5259 (10)	0.3996 (3)	0.3615 (3)	0.0810 (16)
H6	0.6546	0.4199	0.3921	0.097*
C7	0.5168 (12)	0.4142 (3)	0.2759 (3)	0.0918 (18)
H7	0.6369	0.4449	0.2498	0.110*
C8	0.3291 (10)	0.3827 (3)	0.2312 (3)	0.0778 (15)
H8	0.3218	0.3917	0.1744	0.093*
C9	0.1530 (10)	0.3382 (3)	0.2696 (3)	0.0828 (16)
H9	0.0259	0.3166	0.2391	0.099*
C10	0.1640 (10)	0.3252 (3)	0.3547 (3)	0.0723 (14)
H10	0.0433	0.2948	0.3806	0.087*
C11	−0.1670 (8)	0.5573 (3)	0.5071 (3)	0.0559 (11)
C12	−0.0695 (9)	0.5646 (3)	0.4280 (3)	0.0732 (15)
H12	0.0569	0.5306	0.4113	0.088*
C13	−0.1665 (12)	0.6238 (3)	0.3757 (3)	0.0846 (17)
H13	−0.1084	0.6283	0.3219	0.101*
C14	−0.3446 (12)	0.6757 (3)	0.4005 (4)	0.0903 (18)
H14	−0.4065	0.7156	0.3642	0.108*
C15	−0.4343 (10)	0.6694 (3)	0.4799 (4)	0.0843 (17)
H15	−0.5564	0.7051	0.4972	0.101*
C16	−0.3424 (9)	0.6101 (3)	0.5332 (3)	0.0713 (13)
H16	−0.4004	0.6062	0.5870	0.086*
H2	−0.202 (6)	0.480 (3)	0.590 (3)	0.083 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.064 (2)	0.116 (3)	0.0491 (18)	−0.007 (2)	−0.0015 (17)	0.0073 (19)
O2	0.0524 (18)	0.0665 (19)	0.0602 (18)	−0.0005 (17)	−0.0042 (16)	−0.0064 (16)
N1	0.065 (3)	0.077 (3)	0.049 (2)	0.010 (2)	−0.002 (2)	−0.006 (2)
C1	0.051 (3)	0.055 (3)	0.047 (3)	0.000 (2)	−0.005 (2)	0.000 (2)
C2	0.046 (3)	0.083 (3)	0.055 (3)	0.002 (3)	0.003 (2)	0.003 (3)
C3	0.085 (4)	0.104 (4)	0.060 (3)	−0.007 (4)	0.006 (3)	0.019 (3)
C4	0.084 (3)	0.059 (3)	0.050 (3)	0.008 (3)	−0.002 (3)	−0.001 (2)
C5	0.053 (3)	0.053 (2)	0.055 (3)	0.007 (3)	0.008 (2)	0.004 (2)
C6	0.085 (4)	0.093 (4)	0.065 (3)	−0.012 (4)	0.002 (3)	−0.012 (3)
C7	0.104 (5)	0.107 (4)	0.065 (4)	−0.015 (4)	0.011 (4)	0.009 (3)
C8	0.093 (4)	0.085 (4)	0.056 (3)	−0.007 (4)	−0.003 (3)	0.003 (3)
C9	0.090 (4)	0.095 (4)	0.063 (3)	−0.016 (4)	−0.014 (3)	0.001 (3)
C10	0.071 (3)	0.083 (3)	0.063 (3)	−0.011 (3)	−0.002 (3)	0.009 (3)
C11	0.053 (3)	0.067 (3)	0.048 (3)	0.005 (3)	−0.003 (2)	−0.001 (2)
C12	0.075 (4)	0.094 (4)	0.051 (3)	0.004 (3)	0.003 (3)	0.008 (3)
C13	0.104 (4)	0.092 (4)	0.058 (3)	0.010 (4)	−0.003 (3)	0.008 (3)
C14	0.103 (5)	0.079 (4)	0.089 (5)	−0.006 (4)	−0.016 (4)	0.016 (3)
C15	0.080 (4)	0.071 (3)	0.102 (5)	0.020 (3)	−0.002 (4)	−0.012 (3)
C16	0.067 (3)	0.079 (3)	0.067 (3)	0.010 (3)	0.006 (3)	−0.011 (3)

Geometric parameters (Å, º)

O1—C2	1.215 (5)	C7—C8	1.369 (7)
O2—C1	1.406 (4)	C7—H7	0.9300
O2—N1	1.451 (5)	C8—C9	1.361 (7)
N1—C11	1.436 (5)	C8—H8	0.9300
N1—H2	0.86 (2)	C9—C10	1.391 (7)
C1—C2	1.519 (6)	C9—H9	0.9300
C1—C4	1.524 (5)	C10—H10	0.9300
C1—H1	0.9800	C11—C16	1.357 (6)
C2—C3	1.488 (6)	C11—C12	1.394 (6)
C3—H3A	0.9600	C12—C13	1.374 (6)
C3—H3B	0.9600	C12—H12	0.9300
C3—H3C	0.9600	C13—C14	1.353 (7)
C4—C5	1.516 (6)	C13—H13	0.9300
C4—H4A	0.9700	C14—C15	1.380 (7)
C4—H4B	0.9700	C14—H14	0.9300
C5—C10	1.362 (6)	C15—C16	1.374 (7)
C5—C6	1.364 (6)	C15—H15	0.9300
C6—C7	1.404 (6)	C16—H16	0.9300
C6—H6	0.9300
C1—O2—N1	107.4 (3)	C8—C7—C6	119.2 (5)
C11—N1—O2	111.7 (3)	C8—C7—H7	120.4
C11—N1—H2	103 (3)	C6—C7—H7	120.4
O2—N1—H2	103 (3)	C9—C8—C7	120.3 (5)
O2—C1—C2	113.0 (3)	C9—C8—H8	119.9
O2—C1—C4	107.8 (3)	C7—C8—H8	119.9
C2—C1—C4	108.5 (4)	C8—C9—C10	119.7 (5)
O2—C1—H1	109.1	C8—C9—H9	120.2
C2—C1—H1	109.1	C10—C9—H9	120.2
C4—C1—H1	109.1	C5—C10—C9	121.2 (5)
O1—C2—C3	121.7 (4)	C5—C10—H10	119.4
O1—C2—C1	118.5 (4)	C9—C10—H10	119.4
C3—C2—C1	119.7 (4)	C16—C11—C12	121.1 (5)
C2—C3—H3A	109.5	C16—C11—N1	117.5 (4)
C2—C3—H3B	109.5	C12—C11—N1	121.3 (4)
H3A—C3—H3B	109.5	C13—C12—C11	117.8 (5)
C2—C3—H3C	109.5	C13—C12—H12	121.1
H3A—C3—H3C	109.5	C11—C12—H12	121.1
H3B—C3—H3C	109.5	C14—C13—C12	121.5 (5)
C5—C4—C1	113.7 (4)	C14—C13—H13	119.2
C5—C4—H4A	108.8	C12—C13—H13	119.2
C1—C4—H4A	108.8	C13—C14—C15	120.0 (5)
C5—C4—H4B	108.8	C13—C14—H14	120.0
C1—C4—H4B	108.8	C15—C14—H14	120.0
H4A—C4—H4B	107.7	C16—C15—C14	119.6 (5)
C10—C5—C6	118.8 (4)	C16—C15—H15	120.2
C10—C5—C4	122.7 (4)	C14—C15—H15	120.2
C6—C5—C4	118.5 (5)	C11—C16—C15	119.9 (5)
C5—C6—C7	120.8 (5)	C11—C16—H16	120.0
C5—C6—H6	119.6	C15—C16—H16	120.0
C7—C6—H6	119.6
C1—O2—N1—C11	117.7 (4)	C7—C8—C9—C10	0.3 (8)
N1—O2—C1—C2	66.1 (5)	C6—C5—C10—C9	−0.8 (7)
N1—O2—C1—C4	−174.0 (3)	C4—C5—C10—C9	179.3 (5)
O2—C1—C2—O1	−154.9 (4)	C8—C9—C10—C5	−0.1 (8)
C4—C1—C2—O1	85.6 (5)	O2—N1—C11—C16	152.2 (4)
O2—C1—C2—C3	27.9 (6)	O2—N1—C11—C12	−32.1 (6)
C4—C1—C2—C3	−91.6 (5)	C16—C11—C12—C13	−3.7 (7)
O2—C1—C4—C5	63.6 (5)	N1—C11—C12—C13	−179.3 (4)
C2—C1—C4—C5	−173.7 (4)	C11—C12—C13—C14	2.5 (8)
C1—C4—C5—C10	−94.4 (5)	C12—C13—C14—C15	−0.6 (8)
C1—C4—C5—C6	85.7 (5)	C13—C14—C15—C16	−0.2 (8)
C10—C5—C6—C7	1.5 (7)	C12—C11—C16—C15	3.0 (7)
C4—C5—C6—C7	−178.6 (5)	N1—C11—C16—C15	178.8 (4)
C5—C6—C7—C8	−1.3 (8)	C14—C15—C16—C11	−1.0 (7)
C6—C7—C8—C9	0.4 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O1^i	0.86 (2)	2.18 (2)	3.038 (6)	173 (4)

Symmetry code: (i) x−1, y, z.