3-Hydroxy­imino-1-methyl-5-phenyl­cyclo­hexane-1-carbonitrile

In the title mol­ecule, C₁₄H₁₆N₂O, the cyclo­hexane ring adopts a chair conformation. The oxime group has an equatorial orientation. The cyano group and the methyl group have axial and equatorial orientations, respectively. The phenyl ring has an equatorial orientation. The structure is stabilized by inter­molecular O—H...N hydogen bonds and intra­molecular C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 160 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.059
• wR factor = 0.165
• Data-to-parameter ratio = 22.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C3     -   C311    ..       6.58 su

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C5     = ...          R

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

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

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S1. Comment

Related literature were reported by Pandiarajan et al., 1984 and Gurumani et al., 1997.

The present X-ray diffraction study was undertaken to determine how the conformation of the system is affected by the substitution of an oxime moiety at position 3, cyano and methyl groups at position 1 and phenyl ring at position 5 of the cyclohexane. The molecular structure of (I), with atomic numbering scheme is shown in Fig. 1. The cyclohexane ring adopts a chair conformation. The oxime moiety at position 1 is planar and has an equatorial orientation. The cyano group and the methyl group at position 1 have an axial and equatorial orientations, respectively. The phenyl ring at position 5 has an equatorial orientation. The mean plane of atoms C2/C3/C5/C6 and phenyl ring make dihedral angle of 79.92 (6)°. In the crystal structure, the molecules are stabilized by intermolecular O1–H1···N1 hydogen bonds and intramolecular C2–H2B···O1 interactions (Fig. 2).

Related literature

For related literature, see: Gurumani, et al. (1997); Pandiarajan et al. (1984).

S2. Experimental

A mixture of 3-cyano-3-methyl-5-phenylcyclohexanone (2.13 g, 0.01 mol), sodium acetate trihydrate (4.08 g, 0.03 mol), hydroxylamine hydrochloride (1.39 g, 0.02 mol) and ethanol (50 ml) was heated with reflux for 20 m. The reaction mixture was cooled to room temperature and poured into water. The separated solid was filtered off and it was purified by column chromatography (Benzene-EtOAc, 9.5:0.5 v/v). The yield of the isolated product was 2.17 g (87%).

S3. Refinement

H atom bonded to O was located in a difference Fourier map and refined freely. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C–H = 0.93–0.98 Å and U_iso=1.2 or 1.5 times U_eq(C).

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The molecular packing of (I), viewed down the b axis. Dashed lines indicate hydrogen bonds.

3-Hydroxyimino-1-methyl-5-phenylcyclohexane-1-carbonitrile

Crystal data

C14H16N2O	F(000) = 488
Mr = 228.29	Dx = 1.235 Mg m^−3
Monoclinic, P21/n	Melting point: 449 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.6394 (2) Å	Cell parameters from 3701 reflections
b = 14.6658 (5) Å	θ = 2.0–30.0°
c = 12.6653 (3) Å	µ = 0.08 mm^−1
β = 95.146 (2)°	T = 160 K
V = 1228.28 (6) Å^3	Block, colourless
Z = 4	0.25 × 0.25 × 0.25 mm

Data collection

Nonius KappaCCD area-detector diffractometer	2568 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.082
Horizontally mounted graphite crystal monochromator	θmax = 30.0°, θmin = 2.1°
Detector resolution: 9 pixels mm^-1	h = −9→9
φ and ω scans with κ offsets	k = −20→20
33562 measured reflections	l = −17→17
3588 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.165	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0773P)^2 + 0.3782P] where P = (Fo^2 + 2Fc^2)/3
3588 reflections	(Δ/σ)max < 0.001
159 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. Solvent used: n-hexane / EtOAc Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.678 (2) Frames collected: 361 Seconds exposure per frame: 28 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.20084 (18)	0.49328 (7)	−0.06439 (9)	0.0284 (3)
N1	0.13724 (19)	0.41986 (8)	−0.00310 (9)	0.0215 (3)
N311	0.2380 (2)	0.23128 (12)	−0.26976 (11)	0.0412 (5)
C1	0.2597 (2)	0.35272 (9)	0.00221 (11)	0.0194 (4)
C2	0.4533 (2)	0.34800 (10)	−0.04978 (12)	0.0233 (4)
C3	0.4888 (2)	0.25392 (9)	−0.09912 (11)	0.0196 (4)
C4	0.4514 (2)	0.17716 (9)	−0.01999 (11)	0.0192 (4)
C5	0.2397 (2)	0.18121 (9)	0.01813 (10)	0.0178 (4)
C6	0.2112 (2)	0.27419 (9)	0.07144 (11)	0.0209 (4)
C31	0.7058 (2)	0.25006 (11)	−0.13174 (13)	0.0276 (4)
C51	0.1935 (2)	0.10561 (9)	0.09409 (11)	0.0191 (4)
C52	0.3403 (3)	0.06703 (11)	0.16485 (12)	0.0299 (5)
C53	0.2892 (3)	0.00186 (12)	0.23784 (14)	0.0376 (5)
C54	0.0913 (3)	−0.02518 (11)	0.24113 (13)	0.0319 (5)
C55	−0.0553 (3)	0.01230 (12)	0.17107 (14)	0.0346 (5)
C56	−0.0048 (2)	0.07656 (11)	0.09776 (13)	0.0298 (5)
C311	0.3463 (2)	0.24197 (11)	−0.19548 (12)	0.0254 (4)
H1	0.097 (4)	0.5381 (16)	−0.0536 (16)	0.054 (6)*
H2A	0.56521	0.36168	0.00241	0.0279*
H2B	0.45126	0.39411	−0.10477	0.0279*
H4A	0.46953	0.11866	−0.05358	0.0230*
H4B	0.55085	0.18172	0.04073	0.0230*
H5	0.14139	0.17711	−0.04420	0.0213*
H6A	0.07228	0.27958	0.08869	0.0250*
H6B	0.29793	0.27701	0.13721	0.0250*
H31A	0.72880	0.19193	−0.16337	0.0414*
H31B	0.79959	0.25823	−0.07026	0.0414*
H31C	0.72469	0.29761	−0.18200	0.0414*
H52	0.47452	0.08484	0.16364	0.0358*
H53	0.38959	−0.02360	0.28471	0.0451*
H54	0.05733	−0.06836	0.29030	0.0382*
H55	−0.18938	−0.00555	0.17280	0.0415*
H56	−0.10563	0.10071	0.05012	0.0357*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0305 (6)	0.0167 (5)	0.0388 (6)	0.0023 (4)	0.0084 (5)	0.0075 (4)
N1	0.0258 (6)	0.0148 (6)	0.0242 (6)	0.0002 (5)	0.0035 (5)	0.0015 (4)
N311	0.0411 (9)	0.0545 (10)	0.0267 (8)	−0.0099 (7)	−0.0040 (7)	0.0064 (7)
C1	0.0225 (7)	0.0158 (6)	0.0197 (7)	0.0011 (5)	0.0014 (5)	−0.0018 (5)
C2	0.0225 (7)	0.0195 (7)	0.0287 (8)	−0.0002 (6)	0.0068 (6)	0.0003 (6)
C3	0.0195 (7)	0.0208 (7)	0.0187 (7)	0.0024 (5)	0.0032 (5)	−0.0007 (5)
C4	0.0204 (7)	0.0181 (7)	0.0192 (6)	0.0049 (5)	0.0019 (5)	0.0006 (5)
C5	0.0193 (7)	0.0164 (6)	0.0175 (6)	0.0031 (5)	0.0012 (5)	0.0007 (5)
C6	0.0247 (7)	0.0175 (7)	0.0211 (7)	0.0033 (5)	0.0057 (5)	0.0005 (5)
C31	0.0228 (7)	0.0314 (8)	0.0297 (8)	0.0027 (6)	0.0083 (6)	0.0010 (6)
C51	0.0244 (7)	0.0151 (6)	0.0182 (6)	0.0032 (5)	0.0037 (5)	−0.0009 (5)
C52	0.0301 (8)	0.0288 (8)	0.0295 (8)	−0.0012 (7)	−0.0039 (7)	0.0078 (6)
C53	0.0451 (10)	0.0335 (9)	0.0324 (9)	0.0018 (8)	−0.0065 (8)	0.0132 (7)
C54	0.0474 (10)	0.0205 (7)	0.0291 (8)	0.0012 (7)	0.0108 (7)	0.0059 (6)
C55	0.0318 (9)	0.0300 (9)	0.0439 (10)	0.0012 (7)	0.0141 (7)	0.0088 (7)
C56	0.0251 (8)	0.0294 (8)	0.0350 (9)	0.0040 (6)	0.0036 (7)	0.0112 (7)
C311	0.0266 (8)	0.0274 (8)	0.0226 (7)	−0.0014 (6)	0.0051 (6)	0.0036 (6)

Geometric parameters (Å, º)

O1—N1	1.4139 (16)	C54—C55	1.372 (3)
O1—H1	0.97 (3)	C55—C56	1.385 (2)
N1—C1	1.2749 (18)	C2—H2A	0.9700
N311—C311	1.143 (2)	C2—H2B	0.9700
C1—C6	1.4999 (19)	C4—H4A	0.9700
C1—C2	1.4975 (19)	C4—H4B	0.9700
C2—C3	1.542 (2)	C5—H5	0.9800
C3—C4	1.5421 (19)	C6—H6A	0.9700
C3—C31	1.5351 (19)	C6—H6B	0.9700
C3—C311	1.486 (2)	C31—H31A	0.9600
C4—C5	1.5277 (19)	C31—H31B	0.9600
C5—C6	1.5408 (19)	C31—H31C	0.9600
C5—C51	1.5172 (19)	C52—H52	0.9300
C51—C56	1.3886 (19)	C53—H53	0.9300
C51—C52	1.384 (2)	C54—H54	0.9300
C52—C53	1.393 (2)	C55—H55	0.9300
C53—C54	1.377 (3)	C56—H56	0.9300
O1···N1^i	2.7814 (17)	H4A···H31A	2.5500
O1···H2B	2.3000	H4B···C52	2.7700
O1···H1^i	2.62 (2)	H4B···H6B	2.5800
O1···H2A^ii	2.7100	H4B···H31B	2.5300
O1···H53^iii	2.7200	H4B···H52	2.2000
N1···O1^i	2.7814 (17)	H4B···H56^ix	2.5600
N1···N1^i	2.9797 (17)	H4B···N311^x	2.9000
N1···H53^iv	2.9100	H5···C311	2.6300
N1···H1^i	1.88 (3)	H5···H31B^xi	2.5600
N311···H4B^iii	2.9000	H5···H56	2.3900
C56···C56^v	3.348 (2)	H6A···C56	3.0300
C1···H54^iv	3.0200	H6B···H4B	2.5800
C1···H1^i	2.98 (3)	H6B···H54^iv	2.6000
C4···H52	2.6800	H6B···C31^vii	3.0700
C31···H6B^vi	3.0700	H31A···H4A	2.5500
C52···H4B	2.7700	H31A···C53^viii	2.9900
C52···H31C^vii	2.9300	H31A···C54^viii	2.9300
C52···H4A	3.0600	H31B···H2A	2.4100
C53···H31A^viii	2.9900	H31B···H4B	2.5300
C54···H2B^vii	2.9500	H31B···H5^ix	2.5600
C54···H31A^viii	2.9300	H31C···H2B	2.5600
C56···H6A	3.0300	H31C···C52^vi	2.9300
C311···H5	2.6300	H52···C4	2.6800
H1···O1^i	2.62 (2)	H52···H4B	2.2000
H1···N1^i	1.88 (3)	H52···H55^ix	2.5900
H1···C1^i	2.98 (3)	H53···N1^xii	2.9100
H1···H1^i	2.25 (3)	H53···O1^x	2.7200
H1···H53^iii	2.3700	H53···H1^x	2.3700
H2A···H31B	2.4100	H54···C1^xii	3.0200
H2A···O1^ii	2.7100	H54···H6B^xii	2.6000
H2B···O1	2.3000	H55···H52^xi	2.5900
H2B···H31C	2.5600	H56···H4B^xi	2.5600
H2B···C54^vi	2.9500	H56···H5	2.3900
H4A···C52	3.0600
N1—O1—H1	100.8 (14)	C3—C4—H4A	109.00
O1—N1—C1	113.37 (12)	C5—C4—H4B	109.00
N1—C1—C2	125.52 (13)	C3—C4—H4B	109.00
N1—C1—C6	117.04 (12)	C5—C4—H4A	109.00
C2—C1—C6	117.34 (12)	H4A—C4—H4B	108.00
C1—C2—C3	112.84 (11)	C51—C5—H5	108.00
C2—C3—C4	110.52 (11)	C4—C5—H5	108.00
C2—C3—C31	108.87 (11)	C6—C5—H5	108.00
C4—C3—C31	110.96 (11)	C1—C6—H6A	109.00
C4—C3—C311	108.66 (11)	C5—C6—H6B	109.00
C2—C3—C311	109.22 (12)	C1—C6—H6B	109.00
C31—C3—C311	108.57 (12)	C5—C6—H6A	109.00
C3—C4—C5	112.54 (11)	H6A—C6—H6B	108.00
C4—C5—C51	114.59 (11)	C3—C31—H31C	109.00
C6—C5—C51	109.22 (11)	C3—C31—H31A	109.00
C4—C5—C6	109.00 (11)	C3—C31—H31B	109.00
C1—C6—C5	112.47 (11)	H31B—C31—H31C	109.00
C5—C51—C52	122.58 (13)	H31A—C31—H31B	109.00
C5—C51—C56	119.45 (12)	H31A—C31—H31C	109.00
C52—C51—C56	117.88 (14)	C51—C52—H52	120.00
C51—C52—C53	120.73 (17)	C53—C52—H52	120.00
C52—C53—C54	120.52 (17)	C54—C53—H53	120.00
C53—C54—C55	119.26 (16)	C52—C53—H53	120.00
C54—C55—C56	120.39 (17)	C55—C54—H54	120.00
C51—C56—C55	121.23 (15)	C53—C54—H54	120.00
C1—C2—H2B	109.00	C54—C55—H55	120.00
C1—C2—H2A	109.00	C56—C55—H55	120.00
H2A—C2—H2B	108.00	C51—C56—H56	119.00
C3—C2—H2A	109.00	C55—C56—H56	119.00
C3—C2—H2B	109.00	N311—C311—C3	178.81 (17)
O1—N1—C1—C2	−0.2 (2)	C4—C5—C6—C1	52.56 (14)
O1—N1—C1—C6	176.13 (11)	C51—C5—C6—C1	178.44 (11)
N1—C1—C2—C3	−138.80 (14)	C4—C5—C51—C52	32.02 (19)
C6—C1—C2—C3	44.89 (17)	C4—C5—C51—C56	−151.53 (13)
N1—C1—C6—C5	135.74 (13)	C6—C5—C51—C52	−90.56 (16)
C2—C1—C6—C5	−47.64 (16)	C6—C5—C51—C56	85.88 (15)
C1—C2—C3—C4	−47.54 (15)	C5—C51—C52—C53	175.88 (14)
C1—C2—C3—C31	−169.65 (12)	C56—C51—C52—C53	−0.6 (2)
C1—C2—C3—C311	71.95 (15)	C5—C51—C56—C55	−175.43 (14)
C2—C3—C4—C5	56.63 (14)	C52—C51—C56—C55	1.2 (2)
C31—C3—C4—C5	177.51 (11)	C51—C52—C53—C54	−0.2 (3)
C311—C3—C4—C5	−63.20 (14)	C52—C53—C54—C55	0.5 (3)
C3—C4—C5—C6	−58.77 (14)	C53—C54—C55—C56	0.1 (3)
C3—C4—C5—C51	178.53 (11)	C54—C55—C56—C51	−0.9 (3)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x, −y, −z; (vi) x+1/2, −y+1/2, z−1/2; (vii) x−1/2, −y+1/2, z+1/2; (viii) −x+1, −y, −z; (ix) x+1, y, z; (x) x+1/2, −y+1/2, z+1/2; (xi) x−1, y, z; (xii) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^i	0.97 (3)	1.88 (3)	2.7814 (17)	154 (2)
C2—H2B···O1	0.97	2.30	2.7070 (18)	104

Symmetry code: (i) −x, −y+1, −z.