(±)-(cis-8a-Hydr­oxy-2-oxoperhydro­naphthalen-4a-yl)propane­nitrile: hydrogen bonding in a Robinson-annulation inter­mediate

The title racemate, C₁₃H₁₉NO₂, is a pre-dehydration inter­mediate isolated from the base-catalysed Robinson annulation of (+/−)-2-(2-cyano­ethyl)cyclo­hexa­none. Centrosymmetric dimers are formed by reciprocal hydroxyl-to-ketone hydrogen bonding [O...O = 2.7902 (13) Å and O—H...O = 176°]. One inter­molecular C—H...O close contact is found to the hydroxyl group.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.037
• wR factor = 0.096
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.89

Author Response: Even though we collected data out to 0.83 \%A resolution, the crystal diffracted poorly beyond 0.88\%A resolution, where more than 40% of the missing data lie. Larger crystals were not obtainable, and since the crystals of this compound are no longer available, we can only rely on the current data set.

Alert level B
REFLT03_ALERT_3_B  Reflection count < 90% complete (theta max?)
           From the CIF: _diffrn_reflns_theta_max           67.52
           From the CIF: _diffrn_reflns_theta_full          67.52
           From the CIF: _reflns_number_total               1857
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         2084
           Completeness (_total/calc)             89.11%
PLAT022_ALERT_3_B Ratio Unique / Expected Reflections too Low ....       0.89

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C10    -   C11     ..       6.31 su
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         34
            C9  -C10 -C11 -N1    -12.00  3.00   1.555   1.555   1.555   1.555

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

   0 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
   3 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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Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS (Sheldrick, 1997); program(s) used to refine structure: SHELXL (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2004); software used to prepare material for publication: SHELXTL.

[(+/-)-cis-8a-Hydroxy-2-oxoperhydronaphthalen-4a-yl]propanenitrile

Crystal data

C13H19NO2	Z = 2
Mr = 221.29	F(000) = 240
Triclinic, P1	Dx = 1.267 Mg m^−3
Hall symbol: -P 1	Melting point: 424 K
a = 5.8894 (7) Å	Cu Kα radiation, λ = 1.54178 Å
b = 7.6197 (11) Å	Cell parameters from 4494 reflections
c = 13.4112 (17) Å	θ = 3.9–67.5°
α = 91.860 (7)°	µ = 0.68 mm^−1
β = 91.695 (5)°	T = 100 K
γ = 105.246 (6)°	Parallelepiped, colourless
V = 579.89 (13) Å^3	0.33 × 0.24 × 0.15 mm

Data collection

Bruker SMART CCD APEX-II area-detector diffractometer	1857 independent reflections
Radiation source: fine-focus sealed tube	1806 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
φ and ω scans	θmax = 67.5°, θmin = 7.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −6→7
Tmin = 0.82, Tmax = 0.90	k = −7→8
4494 measured reflections	l = −16→15

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0464P)^2 + 0.2474P] where P = (Fo^2 + 2Fc^2)/3
1857 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Experimental. crystal mounted in cryo-loop using Paratone-N

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	0.15443 (16)	0.34594 (13)	0.54817 (7)	0.0234 (3)
N1	1.0427 (2)	0.78309 (17)	1.05313 (9)	0.0285 (3)
C1	0.3281 (2)	0.66174 (18)	0.58954 (9)	0.0183 (3)
H1A	0.2175	0.7394	0.5935	0.022*
H1B	0.3837	0.6641	0.5205	0.022*
O2	0.70665 (15)	0.63478 (13)	0.64918 (6)	0.0205 (2)
H2A	0.7440	0.6358	0.5892	0.031*
C2	0.1998 (2)	0.46981 (18)	0.61164 (9)	0.0181 (3)
C3	0.1273 (2)	0.44154 (18)	0.71733 (9)	0.0186 (3)
H3A	0.0683	0.3095	0.7277	0.022*
H3B	−0.0024	0.4988	0.7300	0.022*
C4	0.3352 (2)	0.52443 (18)	0.79122 (9)	0.0184 (3)
H4A	0.4476	0.4482	0.7881	0.022*
H4B	0.2753	0.5189	0.8596	0.022*
C4A	0.4693 (2)	0.72260 (17)	0.77332 (9)	0.0156 (3)
C5	0.3147 (2)	0.85256 (18)	0.79610 (9)	0.0183 (3)
H5A	0.1662	0.8125	0.7552	0.022*
H5B	0.2739	0.8445	0.8672	0.022*
C6	0.4340 (2)	1.05058 (18)	0.77528 (10)	0.0217 (3)
H6A	0.5755	1.0950	0.8202	0.026*
H6B	0.3247	1.1265	0.7893	0.026*
C7	0.5057 (2)	1.06962 (19)	0.66663 (10)	0.0227 (3)
H7A	0.3626	1.0425	0.6221	0.027*
H7B	0.5962	1.1967	0.6567	0.027*
C8A	0.5417 (2)	0.74165 (18)	0.66270 (9)	0.0169 (3)
C8	0.6555 (2)	0.94041 (19)	0.63877 (9)	0.0203 (3)
H8A	0.8102	0.9818	0.6752	0.024*
H8B	0.6839	0.9469	0.5664	0.024*
C9	0.6951 (2)	0.76886 (18)	0.84159 (9)	0.0171 (3)
H9A	0.7817	0.6758	0.8287	0.021*
H9B	0.7971	0.8877	0.8230	0.021*
C10	0.6524 (2)	0.7784 (2)	0.95417 (9)	0.0213 (3)
H10A	0.6017	0.8893	0.9711	0.026*
H10B	0.5257	0.6712	0.9715	0.026*
C11	0.8698 (2)	0.78198 (18)	1.01152 (9)	0.0215 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0220 (5)	0.0249 (6)	0.0225 (5)	0.0058 (4)	−0.0010 (4)	−0.0052 (4)
N1	0.0263 (7)	0.0321 (7)	0.0237 (6)	0.0015 (5)	−0.0051 (5)	0.0063 (5)
C1	0.0177 (6)	0.0229 (8)	0.0155 (6)	0.0077 (5)	−0.0005 (5)	0.0007 (5)
O2	0.0188 (5)	0.0289 (6)	0.0172 (4)	0.0121 (4)	0.0014 (3)	−0.0012 (4)
C2	0.0120 (6)	0.0235 (8)	0.0205 (6)	0.0085 (5)	−0.0027 (5)	−0.0015 (5)
C3	0.0170 (6)	0.0173 (7)	0.0211 (6)	0.0038 (5)	−0.0001 (5)	0.0006 (5)
C4	0.0184 (6)	0.0192 (7)	0.0179 (6)	0.0055 (5)	−0.0005 (5)	0.0024 (5)
C4A	0.0146 (6)	0.0170 (7)	0.0159 (6)	0.0052 (5)	0.0004 (5)	0.0008 (5)
C5	0.0160 (6)	0.0225 (8)	0.0177 (6)	0.0075 (5)	0.0004 (5)	0.0000 (5)
C6	0.0229 (7)	0.0197 (8)	0.0246 (7)	0.0098 (5)	−0.0018 (5)	−0.0008 (5)
C7	0.0266 (7)	0.0179 (8)	0.0228 (7)	0.0045 (5)	−0.0040 (5)	0.0043 (5)
C8A	0.0146 (6)	0.0207 (7)	0.0171 (6)	0.0074 (5)	0.0009 (5)	0.0005 (5)
C8	0.0186 (6)	0.0244 (8)	0.0164 (6)	0.0027 (5)	0.0000 (5)	0.0038 (5)
C9	0.0153 (6)	0.0204 (7)	0.0165 (6)	0.0060 (5)	0.0005 (5)	0.0012 (5)
C10	0.0191 (6)	0.0263 (8)	0.0174 (6)	0.0045 (5)	−0.0003 (5)	0.0002 (5)
C11	0.0248 (7)	0.0208 (8)	0.0163 (6)	0.0012 (5)	0.0016 (5)	0.0028 (5)

Geometric parameters (Å, º)

O1—C2	1.2202 (16)	C5—C6	1.5263 (18)
N1—C11	1.1441 (18)	C5—H5A	0.9900
C1—C2	1.5026 (18)	C5—H5B	0.9900
C1—C8A	1.5493 (17)	C6—C7	1.5298 (18)
C1—H1A	0.9900	C6—H6A	0.9900
C1—H1B	0.9900	C6—H6B	0.9900
O2—C8A	1.4342 (15)	C7—C8	1.5294 (19)
O2—H2A	0.8400	C7—H7A	0.9900
C2—C3	1.4984 (17)	C7—H7B	0.9900
C3—C4	1.5365 (17)	C8A—C8	1.5350 (18)
C3—H3A	0.9900	C8—H8A	0.9900
C3—H3B	0.9900	C8—H8B	0.9900
C4—C4A	1.5393 (18)	C9—C10	1.5405 (17)
C4—H4A	0.9900	C9—H9A	0.9900
C4—H4B	0.9900	C9—H9B	0.9900
C4A—C5	1.5407 (18)	C10—C11	1.4674 (18)
C4A—C9	1.5465 (16)	C10—H10A	0.9900
C4A—C8A	1.5564 (16)	C10—H10B	0.9900
C2—C1—C8A	112.58 (10)	C7—C6—H6A	109.5
C2—C1—H1A	109.1	C5—C6—H6B	109.5
C8A—C1—H1A	109.1	C7—C6—H6B	109.5
C2—C1—H1B	109.1	H6A—C6—H6B	108.0
C8A—C1—H1B	109.1	C8—C7—C6	111.24 (10)
H1A—C1—H1B	107.8	C8—C7—H7A	109.4
C8A—O2—H2A	109.5	C6—C7—H7A	109.4
O1—C2—C3	122.13 (12)	C8—C7—H7B	109.4
O1—C2—C1	122.74 (11)	C6—C7—H7B	109.4
C3—C2—C1	115.12 (11)	H7A—C7—H7B	108.0
C2—C3—C4	110.99 (10)	O2—C8A—C8	110.03 (10)
C2—C3—H3A	109.4	O2—C8A—C1	107.55 (10)
C4—C3—H3A	109.4	C8—C8A—C1	109.47 (10)
C2—C3—H3B	109.4	O2—C8A—C4A	106.28 (9)
C4—C3—H3B	109.4	C8—C8A—C4A	111.98 (10)
H3A—C3—H3B	108.0	C1—C8A—C4A	111.40 (10)
C3—C4—C4A	115.21 (10)	C7—C8—C8A	113.44 (10)
C3—C4—H4A	108.5	C7—C8—H8A	108.9
C4A—C4—H4A	108.5	C8A—C8—H8A	108.9
C3—C4—H4B	108.5	C7—C8—H8B	108.9
C4A—C4—H4B	108.5	C8A—C8—H8B	108.9
H4A—C4—H4B	107.5	H8A—C8—H8B	107.7
C4—C4A—C5	110.68 (10)	C10—C9—C4A	114.81 (10)
C4—C4A—C9	107.29 (9)	C10—C9—H9A	108.6
C5—C4A—C9	111.27 (10)	C4A—C9—H9A	108.6
C4—C4A—C8A	110.13 (10)	C10—C9—H9B	108.6
C5—C4A—C8A	108.77 (10)	C4A—C9—H9B	108.6
C9—C4A—C8A	108.68 (9)	H9A—C9—H9B	107.5
C6—C5—C4A	113.22 (10)	C11—C10—C9	109.76 (10)
C6—C5—H5A	108.9	C11—C10—H10A	109.7
C4A—C5—H5A	108.9	C9—C10—H10A	109.7
C6—C5—H5B	108.9	C11—C10—H10B	109.7
C4A—C5—H5B	108.9	C9—C10—H10B	109.7
H5A—C5—H5B	107.7	H10A—C10—H10B	108.2
C5—C6—C7	110.94 (11)	N1—C11—C10	177.52 (14)
C5—C6—H6A	109.5
C8A—C1—C2—O1	−128.42 (12)	C5—C4A—C8A—O2	173.35 (10)
C8A—C1—C2—C3	52.61 (14)	C9—C4A—C8A—O2	52.06 (13)
O1—C2—C3—C4	131.13 (12)	C4—C4A—C8A—C8	174.62 (10)
C1—C2—C3—C4	−49.88 (14)	C5—C4A—C8A—C8	53.16 (13)
C2—C3—C4—C4A	50.16 (15)	C9—C4A—C8A—C8	−68.12 (13)
C3—C4—C4A—C5	68.55 (13)	C4—C4A—C8A—C1	51.66 (13)
C3—C4—C4A—C9	−169.88 (10)	C5—C4A—C8A—C1	−69.80 (13)
C3—C4—C4A—C8A	−51.76 (14)	C9—C4A—C8A—C1	168.92 (10)
C4—C4A—C5—C6	−177.43 (10)	C6—C7—C8—C8A	52.56 (14)
C9—C4A—C5—C6	63.37 (13)	O2—C8A—C8—C7	−171.06 (10)
C8A—C4A—C5—C6	−56.32 (13)	C1—C8A—C8—C7	70.96 (13)
C4A—C5—C6—C7	57.37 (14)	C4A—C8A—C8—C7	−53.09 (13)
C5—C6—C7—C8	−53.56 (14)	C4—C4A—C9—C10	−67.90 (13)
C2—C1—C8A—O2	63.36 (13)	C5—C4A—C9—C10	53.31 (14)
C2—C1—C8A—C8	−177.11 (10)	C8A—C4A—C9—C10	173.05 (11)
C2—C1—C8A—C4A	−52.73 (14)	C4A—C9—C10—C11	167.38 (11)
C4—C4A—C8A—O2	−65.20 (12)	C9—C10—C11—N1	−12 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1^i	0.84	1.95	2.7902 (13)	176
C3—H3B···O2^ii	0.99	2.47	3.3184 (15)	144

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