2-[Hydr­oxy(4-nitro­phen­yl)meth­yl]-4-methyl­cyclo­hexa­none

In the title compound, C₁₄H₁₇NO₄, the cyclo­hexane ring displays a chair conformation. The crystal packing is stabilized by O—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.069
• wR factor = 0.205
• Data-to-parameter ratio = 7.6

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.124
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.12
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.59
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        300 Ang.
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9

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           25.20
           From the CIF: _reflns_number_total               1321
           Count of symmetry unique reflns         1344
           Completeness (_total/calc)             98.29%
           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 C7     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C12    = .          S
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
   5 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 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

---

S1. Comment

Beta-hydroxy ketone can be transferred to a large variety of important product. The title compound, (I), is an very important intermediate for the construction of α,β-unsaturated carbonyl compound, which are important synthetic building blocks for the construction of many natural products (Basavaiah et al., 1996). We report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The benzene ring and nitro group is slightly non-planar, with a dihedral angle of 4.14 (8)°. The dihedral angle between the benzene and O4/C8/C9/C10 planes is 11.1 (3)°. The crystal packing is stabilized by O—H···O hydrogen bonding (Table 1).

Related literature

For general background, see: Basavaiah et al. (1996).

S2. Experimental

To a solution of 4-nitrobenzaldehyde (0.5 mmol) and 4-methylcyclohexanone (5 mmol) in anhydrous dicloromethane (2 ml) was added L—N-phenylpyrrolidine-2-carboxamide (19 mg, 0.1 mmol). The resulting mixture was stirred at 273 K for 24 h. The reaction mixture was treated with saturated ammonium chloride solution and the aqueous layer was extracted with ethyl acetate, dried over anhydrous MgSO₄. After filtration and removal of solvent under reduced pressure, the residue was purified through column chromatography on silica gel to give the title compound. Colourless single crystals of the title compound were obtained by recrystallization from an ethanol solution.

S3. Refinement

Hydroxy and methyl H atoms were placed in calculated positions with O—H = 0.82 and C—H = 0.96 Å, and torsion angles were refined, U_iso(H) = 1.5U_eq(O,C). Other H atoms were placed in calculated positions with C—H = 0.93 to 0.98 Å and refined using a riding model with U_iso(H) =1.2U_eq(C). In the absence of significant anomalous scattering effects, Friedel pairs were averaged.

Computing details

Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

2-[Hydroxy(4-nitrophenyl)methyl]-4-methylcyclohexanone

Crystal data

C14H17NO4	F(000) = 280
Mr = 263.29	Dx = 1.283 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 28 reflections
a = 9.917 (3) Å	θ = 4.9–9.2°
b = 6.927 (3) Å	µ = 0.09 mm^−1
c = 10.518 (3) Å	T = 293 K
β = 109.35 (3)°	Block, colourless
V = 681.7 (4) Å^3	0.25 × 0.20 × 0.18 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.124
Radiation source: fine-focus sealed tube	θmax = 25.2°, θmin = 2.0°
Graphite monochromator	h = −11→0
ω/2θ scans	k = −8→8
2439 measured reflections	l = −11→12
1321 independent reflections	3 standard reflections every 300 reflections
773 reflections with I > 2σ(I)	intensity decay: 0.6%

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.205	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.1226P)^2] where P = (Fo^2 + 2Fc^2)/3
1321 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.28 e Å^−3
1 restraint	Δρmin = −0.22 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	0.3277 (6)	−0.0005 (10)	0.9818 (5)	0.0900 (17)
O2	0.2949 (8)	0.2523 (11)	1.0846 (6)	0.112 (2)
O3	0.4801 (5)	0.7878 (7)	0.6164 (5)	0.0666 (12)
H3	0.5562	0.7380	0.6605	0.100*
O4	0.2824 (6)	1.0356 (8)	0.3885 (5)	0.0797 (15)
N	0.3154 (6)	0.1751 (11)	0.9901 (5)	0.0728 (19)
C1	0.3416 (7)	0.6009 (11)	0.7890 (6)	0.0640 (18)
H1	0.3413	0.7348	0.7957	0.077*
C2	0.3250 (7)	0.4906 (10)	0.8923 (6)	0.0621 (17)
H2	0.3114	0.5478	0.9671	0.075*
C3	0.3294 (6)	0.2947 (11)	0.8807 (6)	0.0546 (15)
C4	0.3480 (7)	0.2079 (9)	0.7711 (6)	0.0615 (18)
H4	0.3524	0.0741	0.7664	0.074*
C5	0.3602 (7)	0.3203 (10)	0.6679 (6)	0.0581 (16)
H5	0.3696	0.2616	0.5917	0.070*
C6	0.3587 (6)	0.5168 (9)	0.6757 (5)	0.0493 (14)
C7	0.3760 (6)	0.6408 (9)	0.5629 (6)	0.0491 (14)
H7	0.4063	0.5594	0.5011	0.059*
C8	0.2362 (6)	0.7441 (9)	0.4842 (6)	0.0562 (16)
H8	0.2112	0.8309	0.5465	0.067*
C9	0.2614 (6)	0.8666 (10)	0.3738 (6)	0.0573 (16)
C10	0.2588 (9)	0.7609 (13)	0.2488 (7)	0.078 (2)
H10A	0.3451	0.6842	0.2680	0.094*
H10B	0.2581	0.8539	0.1797	0.094*
C11	0.1309 (8)	0.6310 (13)	0.1962 (6)	0.0726 (19)
H11A	0.1376	0.5592	0.1194	0.087*
H11B	0.0449	0.7090	0.1660	0.087*
C12	0.1203 (6)	0.4908 (11)	0.3032 (6)	0.0654 (17)
H12	0.2088	0.4152	0.3332	0.078*
C13	0.1114 (6)	0.6068 (11)	0.4240 (6)	0.0636 (17)
H13A	0.0235	0.6810	0.3962	0.076*
H13B	0.1067	0.5175	0.4935	0.076*
C14	−0.0036 (9)	0.3504 (14)	0.2514 (9)	0.093 (3)
H14A	0.0054	0.2806	0.1757	0.140*
H14B	−0.0921	0.4206	0.2240	0.140*
H14C	−0.0025	0.2613	0.3216	0.140*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.120 (4)	0.083 (4)	0.070 (3)	−0.017 (3)	0.035 (3)	0.020 (3)
O2	0.166 (6)	0.118 (5)	0.080 (4)	0.025 (5)	0.078 (4)	0.025 (4)
O3	0.065 (2)	0.069 (3)	0.067 (3)	−0.009 (2)	0.025 (2)	0.009 (2)
O4	0.104 (4)	0.053 (3)	0.078 (3)	−0.001 (3)	0.024 (3)	0.013 (3)
N	0.086 (4)	0.089 (6)	0.050 (3)	0.005 (3)	0.031 (3)	0.022 (3)
C1	0.080 (4)	0.063 (4)	0.055 (4)	0.017 (3)	0.031 (3)	0.007 (3)
C2	0.084 (4)	0.066 (5)	0.045 (3)	0.008 (4)	0.032 (3)	0.008 (3)
C3	0.053 (3)	0.068 (5)	0.044 (3)	−0.004 (3)	0.018 (3)	0.012 (3)
C4	0.076 (4)	0.051 (4)	0.057 (4)	−0.005 (3)	0.022 (3)	0.008 (3)
C5	0.080 (4)	0.054 (4)	0.047 (3)	−0.007 (3)	0.031 (3)	−0.002 (3)
C6	0.054 (3)	0.051 (4)	0.048 (3)	0.002 (3)	0.023 (3)	0.004 (3)
C7	0.059 (3)	0.045 (3)	0.049 (3)	0.004 (3)	0.026 (3)	0.005 (3)
C8	0.073 (4)	0.053 (4)	0.051 (3)	0.009 (3)	0.033 (3)	0.005 (3)
C9	0.066 (4)	0.059 (5)	0.050 (3)	0.009 (3)	0.023 (3)	0.015 (3)
C10	0.106 (5)	0.090 (6)	0.054 (4)	−0.017 (5)	0.047 (4)	0.006 (4)
C11	0.081 (4)	0.085 (5)	0.052 (4)	0.006 (4)	0.022 (3)	0.005 (4)
C12	0.062 (3)	0.070 (5)	0.062 (4)	−0.006 (4)	0.020 (3)	0.003 (3)
C13	0.063 (4)	0.073 (5)	0.059 (4)	0.006 (3)	0.027 (3)	0.017 (3)
C14	0.083 (5)	0.085 (6)	0.105 (6)	−0.022 (4)	0.022 (4)	−0.009 (5)

Geometric parameters (Å, º)

O1—N	1.229 (8)	C8—C13	1.523 (9)
O2—N	1.204 (8)	C8—C9	1.524 (8)
O3—C7	1.426 (8)	C8—H8	0.9800
O3—H3	0.8200	C9—C10	1.498 (9)
O4—C9	1.190 (9)	C10—C11	1.503 (11)
N—C3	1.461 (8)	C10—H10A	0.9700
C1—C2	1.382 (9)	C10—H10B	0.9700
C1—C6	1.387 (8)	C11—C12	1.516 (9)
C1—H1	0.9300	C11—H11A	0.9700
C2—C3	1.364 (10)	C11—H11B	0.9700
C2—H2	0.9300	C12—C14	1.519 (10)
C3—C4	1.366 (9)	C12—C13	1.531 (9)
C4—C5	1.373 (9)	C12—H12	0.9800
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.365 (9)	C13—H13B	0.9700
C5—H5	0.9300	C14—H14A	0.9600
C6—C7	1.520 (7)	C14—H14B	0.9600
C7—C8	1.535 (8)	C14—H14C	0.9600
C7—H7	0.9800
C7—O3—H3	109.5	O4—C9—C10	123.1 (6)
O2—N—O1	123.1 (6)	O4—C9—C8	120.9 (6)
O2—N—C3	119.0 (7)	C10—C9—C8	116.0 (6)
O1—N—C3	117.9 (6)	C9—C10—C11	112.5 (5)
C2—C1—C6	121.6 (7)	C9—C10—H10A	109.1
C2—C1—H1	119.2	C11—C10—H10A	109.1
C6—C1—H1	119.2	C9—C10—H10B	109.1
C3—C2—C1	117.7 (6)	C11—C10—H10B	109.1
C3—C2—H2	121.2	H10A—C10—H10B	107.8
C1—C2—H2	121.2	C10—C11—C12	111.6 (5)
C2—C3—C4	122.0 (6)	C10—C11—H11A	109.3
C2—C3—N	118.6 (6)	C12—C11—H11A	109.3
C4—C3—N	119.4 (6)	C10—C11—H11B	109.3
C3—C4—C5	119.4 (6)	C12—C11—H11B	109.3
C3—C4—H4	120.3	H11A—C11—H11B	108.0
C5—C4—H4	120.3	C11—C12—C14	113.0 (6)
C6—C5—C4	120.8 (6)	C11—C12—C13	108.5 (6)
C6—C5—H5	119.6	C14—C12—C13	111.9 (5)
C4—C5—H5	119.6	C11—C12—H12	107.8
C5—C6—C1	118.6 (6)	C14—C12—H12	107.8
C5—C6—C7	120.7 (5)	C13—C12—H12	107.8
C1—C6—C7	120.8 (6)	C8—C13—C12	114.3 (4)
O3—C7—C6	110.5 (5)	C8—C13—H13A	108.7
O3—C7—C8	106.6 (5)	C12—C13—H13A	108.7
C6—C7—C8	111.6 (4)	C8—C13—H13B	108.7
O3—C7—H7	109.4	C12—C13—H13B	108.7
C6—C7—H7	109.4	H13A—C13—H13B	107.6
C8—C7—H7	109.4	C12—C14—H14A	109.5
C13—C8—C9	110.3 (5)	C12—C14—H14B	109.5
C13—C8—C7	113.4 (5)	H14A—C14—H14B	109.5
C9—C8—C7	108.9 (4)	C12—C14—H14C	109.5
C13—C8—H8	108.0	H14A—C14—H14C	109.5
C9—C8—H8	108.0	H14B—C14—H14C	109.5
C7—C8—H8	108.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4^i	0.82	2.31	2.947 (7)	135
O3—H3···O2^ii	0.82	2.60	3.206 (8)	132

Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+2.