A (1R,2R,5R)-(+)-2α-hydroxy­pinan-3-one ketimine

The title compound {systematic name: (1R,2R,5R)-(+)-2-hydr­oxy-2,6,6-trimethyl-3-[(3-pyrid­yl)methyl­imino]­bicyclo[3.1.1]­heptane}, C₁₆H₂₂N₂O, was obtained by the condensation reaction of (1R,2R,5R)-(+)-2α-hydroxy­pinan-3-one with 3-(amino­meth­yl)pyridine in the presence of boron trifluoride. The compound was obtained as an enantiomerically pure isomer, and has the 1R,2R,5R configuration. In the crystal structure, mol­ecules are linked together by inter­molecular O—H...N hydrogen bonds between the hydr­oxy group of the pinanone group and the N atom of the pyridine ring, forming mol­ecular chains.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.109
• Data-to-parameter ratio = 9.1

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are meaningless.
           From the CIF: _refine_ls_abs_structure_Flack    0.200
           From the CIF: _refine_ls_abs_structure_Flack_su    2.100
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ...       2.00
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       2.00

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           26.00
           From the CIF: _reflns_number_total               1613
           Count of symmetry unique reflns         1613
           Completeness (_total/calc)            100.00%
           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

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 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
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELX97-2 (Sheldrick, 1997) and local procedures.

(1R,2R,5R)-2-hydroxy-2,6,6-trimethyl-3-[(3- pyridyl)methylimino]bicyclo[3.1.1]heptane

Crystal data

C16H22N2O	F(000) = 560
Mr = 258.36	Dx = 1.212 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7956 reflections
a = 7.2196 (5) Å	θ = 1.0–27.5°
b = 12.9481 (9) Å	µ = 0.08 mm^−1
c = 15.1436 (9) Å	T = 173 K
V = 1415.63 (16) Å^3	Block, colorless
Z = 4	0.30 × 0.16 × 0.09 mm

Data collection

Nonius KappaCCD diffractometer	1115 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.069
Graphite monochromator	θmax = 26.0°, θmin = 2.1°
Detector resolution: 18 pixels mm^-1	h = −8→8
ω scans at fixed χ = 55°	k = −13→15
7664 measured reflections	l = −18→18
1613 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.047	w = 1/[σ^2(Fo^2) + (0.0541P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.109	(Δ/σ)max = 0.006
S = 1.02	Δρmax = 0.22 e Å^−3
1613 reflections	Δρmin = −0.18 e Å^−3
177 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.009 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.2 (21)

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.

The model was refined as the R,R,R enantiomer as this was known from the synthesis and starting materials of known chirality. All refinement except the final cycles of least-squares were done using unmerged Friedel pairs (Flack and Bernardinelli, 1999, section 4.4). To conform to Acta E editorial policy the Friedel pairs were merged for the final cycles. The Flack parameter was refined using unmerged data, and is given here merely to indicate that the inversion distinguishing power of the data are very weak, as expected.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.2677 (3)	0.07790 (17)	−0.06021 (14)	0.0351 (6)
C2	0.2678 (4)	0.1813 (2)	−0.05621 (17)	0.0347 (8)
H2	0.2826	0.2182	−0.1100	0.042*
C3	0.2478 (4)	0.2382 (2)	0.02070 (16)	0.0287 (7)
C4	0.2300 (4)	0.1827 (2)	0.09883 (16)	0.0325 (7)
H4	0.2180	0.2178	0.1536	0.039*
C5	0.2299 (4)	0.0757 (2)	0.09612 (17)	0.0335 (7)
H5	0.2173	0.0365	0.1488	0.040*
C6	0.2482 (4)	0.0276 (2)	0.01596 (18)	0.0349 (7)
H6	0.2469	−0.0457	0.0147	0.042*
C7	0.2508 (4)	0.3544 (2)	0.01833 (17)	0.0321 (7)
H7A	0.3760	0.3782	0.0012	0.039*
H7B	0.1622	0.3791	−0.0268	0.039*
N8	0.2020 (3)	0.39826 (17)	0.10371 (13)	0.0313 (6)
C9	0.1907 (4)	0.4960 (2)	0.11154 (16)	0.0276 (7)
C10	0.1248 (4)	0.5379 (2)	0.20174 (18)	0.0299 (7)
C11	0.1416 (4)	0.6551 (2)	0.20237 (19)	0.0299 (7)
H11	0.1080	0.6882	0.2598	0.036*
C12	0.0382 (4)	0.6991 (2)	0.12162 (18)	0.0380 (8)
H12A	−0.0009	0.7720	0.1281	0.046*
H12B	−0.0649	0.6552	0.1003	0.046*
C13	0.2211 (4)	0.6845 (2)	0.07057 (18)	0.0349 (8)
H13	0.2491	0.7383	0.0251	0.042*
C14	0.2306 (4)	0.5731 (2)	0.03871 (17)	0.0328 (8)
H14A	0.1398	0.5632	−0.0096	0.039*
H14B	0.3555	0.5595	0.0144	0.039*
C15	0.3248 (4)	0.6966 (2)	0.16003 (18)	0.0336 (7)
C16	0.5086 (4)	0.6406 (2)	0.1701 (2)	0.0438 (9)
H16A	0.6003	0.6714	0.1304	0.066*
H16B	0.4924	0.5675	0.1553	0.066*
H16C	0.5516	0.6467	0.2313	0.066*
C17	0.3554 (5)	0.8102 (2)	0.1837 (2)	0.0490 (9)
H17A	0.4413	0.8413	0.1413	0.074*
H17B	0.4078	0.8150	0.2433	0.074*
H17C	0.2368	0.8469	0.1818	0.074*
C18	0.2261 (5)	0.4880 (2)	0.27828 (16)	0.0420 (9)
H18A	0.2170	0.4127	0.2733	0.063*
H18B	0.1701	0.5105	0.3340	0.063*
H18C	0.3567	0.5086	0.2770	0.063*
O19	−0.0676 (3)	0.51187 (17)	0.21344 (12)	0.0444 (6)
H19	−0.1064	0.4808	0.1684	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0373 (16)	0.0332 (15)	0.0349 (14)	−0.0042 (13)	0.0048 (13)	−0.0057 (11)
C2	0.0359 (19)	0.0397 (19)	0.0285 (15)	−0.0066 (16)	0.0051 (15)	0.0007 (14)
C3	0.0264 (16)	0.0339 (17)	0.0256 (15)	−0.0028 (14)	−0.0017 (15)	−0.0037 (13)
C4	0.0349 (18)	0.0375 (18)	0.0252 (15)	0.0032 (15)	0.0034 (15)	−0.0006 (13)
C5	0.0368 (18)	0.0327 (18)	0.0311 (16)	0.0042 (15)	0.0032 (16)	0.0018 (13)
C6	0.0318 (16)	0.0320 (17)	0.0408 (17)	−0.0004 (15)	0.0021 (17)	−0.0013 (14)
C7	0.0371 (17)	0.0311 (16)	0.0281 (15)	−0.0021 (15)	0.0048 (17)	0.0010 (12)
N8	0.0370 (15)	0.0314 (14)	0.0254 (12)	−0.0020 (12)	0.0005 (12)	−0.0028 (11)
C9	0.0250 (16)	0.0329 (17)	0.0250 (14)	−0.0033 (13)	−0.0035 (13)	0.0009 (14)
C10	0.0299 (16)	0.0328 (17)	0.0271 (15)	−0.0038 (14)	−0.0004 (14)	−0.0026 (14)
C11	0.0311 (18)	0.0299 (17)	0.0286 (15)	0.0046 (13)	0.0014 (14)	−0.0019 (14)
C12	0.0360 (18)	0.0374 (18)	0.0407 (16)	0.0082 (16)	0.0007 (15)	−0.0005 (15)
C13	0.043 (2)	0.0288 (17)	0.0333 (15)	0.0026 (16)	0.0035 (15)	0.0017 (13)
C14	0.0375 (19)	0.0361 (18)	0.0249 (14)	−0.0008 (15)	0.0017 (15)	0.0000 (12)
C15	0.0348 (17)	0.0280 (16)	0.0381 (16)	−0.0046 (14)	0.0041 (15)	−0.0028 (14)
C16	0.0326 (19)	0.051 (2)	0.048 (2)	−0.0042 (15)	0.0004 (17)	−0.0050 (16)
C17	0.059 (2)	0.0374 (19)	0.050 (2)	−0.0104 (17)	0.0097 (19)	−0.0011 (17)
C18	0.063 (2)	0.0371 (18)	0.0255 (15)	−0.0016 (17)	−0.0004 (17)	0.0026 (14)
O19	0.0386 (14)	0.0630 (16)	0.0315 (11)	−0.0182 (10)	0.0088 (10)	−0.0181 (11)

Geometric parameters (Å, º)

N1—C6	1.332 (3)	C11—H11	1.0000
N1—C2	1.340 (3)	C12—C13	1.542 (4)
C2—C3	1.386 (4)	C12—H12A	0.9900
C2—H2	0.9500	C12—H12B	0.9900
C3—C4	1.390 (4)	C13—C14	1.522 (4)
C3—C7	1.505 (4)	C13—C15	1.556 (4)
C4—C5	1.386 (3)	C13—H13	1.0000
C4—H4	0.9500	C14—H14A	0.9900
C5—C6	1.371 (4)	C14—H14B	0.9900
C5—H5	0.9500	C15—C16	1.520 (4)
C6—H6	0.9500	C15—C17	1.530 (4)
C7—N8	1.456 (3)	C16—H16A	0.9800
C7—H7A	0.9900	C16—H16B	0.9800
C7—H7B	0.9900	C16—H16C	0.9800
N8—C9	1.274 (3)	C17—H17A	0.9800
C9—C14	1.515 (3)	C17—H17B	0.9800
C9—C10	1.544 (4)	C17—H17C	0.9800
C10—O19	1.441 (3)	C18—H18A	0.9800
C10—C18	1.515 (4)	C18—H18B	0.9800
C10—C11	1.523 (3)	C18—H18C	0.9800
C11—C12	1.542 (4)	O19—H19	0.8400
C11—C15	1.565 (4)
C6—N1—C2	116.7 (2)	C11—C12—H12B	114.2
N1—C2—C3	124.7 (3)	C13—C12—H12B	114.2
N1—C2—H2	117.7	H12A—C12—H12B	111.4
C3—C2—H2	117.7	C14—C13—C12	108.3 (3)
C2—C3—C4	116.7 (2)	C14—C13—C15	110.5 (2)
C2—C3—C7	120.7 (2)	C12—C13—C15	87.9 (2)
C4—C3—C7	122.6 (2)	C14—C13—H13	115.6
C5—C4—C3	119.4 (2)	C12—C13—H13	115.6
C5—C4—H4	120.3	C15—C13—H13	115.6
C3—C4—H4	120.3	C9—C14—C13	112.6 (2)
C6—C5—C4	118.7 (2)	C9—C14—H14A	109.1
C6—C5—H5	120.6	C13—C14—H14A	109.1
C4—C5—H5	120.6	C9—C14—H14B	109.1
N1—C6—C5	123.7 (3)	C13—C14—H14B	109.1
N1—C6—H6	118.1	H14A—C14—H14B	107.8
C5—C6—H6	118.1	C16—C15—C17	108.0 (2)
N8—C7—C3	111.4 (2)	C16—C15—C13	117.4 (2)
N8—C7—H7A	109.3	C17—C15—C13	111.7 (2)
C3—C7—H7A	109.3	C16—C15—C11	122.2 (2)
N8—C7—H7B	109.3	C17—C15—C11	110.8 (2)
C3—C7—H7B	109.3	C13—C15—C11	85.2 (2)
H7A—C7—H7B	108.0	C15—C16—H16A	109.5
C9—N8—C7	119.1 (2)	C15—C16—H16B	109.5
N8—C9—C14	125.0 (2)	H16A—C16—H16B	109.5
N8—C9—C10	116.8 (2)	C15—C16—H16C	109.5
C14—C9—C10	118.1 (2)	H16A—C16—H16C	109.5
O19—C10—C18	105.8 (2)	H16B—C16—H16C	109.5
O19—C10—C11	108.0 (2)	C15—C17—H17A	109.5
C18—C10—C11	112.4 (2)	C15—C17—H17B	109.5
O19—C10—C9	108.9 (2)	H17A—C17—H17B	109.5
C18—C10—C9	112.3 (2)	C15—C17—H17C	109.5
C11—C10—C9	109.3 (2)	H17A—C17—H17C	109.5
C10—C11—C12	108.9 (2)	H17B—C17—H17C	109.5
C10—C11—C15	114.0 (2)	C10—C18—H18A	109.5
C12—C11—C15	87.6 (2)	C10—C18—H18B	109.5
C10—C11—H11	114.5	H18A—C18—H18B	109.5
C12—C11—H11	114.5	C10—C18—H18C	109.5
C15—C11—H11	114.5	H18A—C18—H18C	109.5
C11—C12—C13	86.4 (2)	H18B—C18—H18C	109.5
C11—C12—H12A	114.2	C10—O19—H19	109.5
C13—C12—H12A	114.2
C6—N1—C2—C3	−0.5 (5)	C18—C10—C11—C15	83.0 (3)
N1—C2—C3—C4	1.2 (5)	C9—C10—C11—C15	−42.4 (3)
N1—C2—C3—C7	179.7 (3)	C10—C11—C12—C13	−87.8 (2)
C2—C3—C4—C5	−1.1 (4)	C15—C11—C12—C13	26.8 (2)
C7—C3—C4—C5	−179.5 (3)	C11—C12—C13—C14	83.9 (2)
C3—C4—C5—C6	0.3 (4)	C11—C12—C13—C15	−27.0 (2)
C2—N1—C6—C5	−0.4 (5)	N8—C9—C14—C13	−175.0 (3)
C4—C5—C6—N1	0.5 (5)	C10—C9—C14—C13	7.1 (4)
C2—C3—C7—N8	172.0 (3)	C12—C13—C14—C9	−49.6 (3)
C4—C3—C7—N8	−9.6 (4)	C15—C13—C14—C9	45.1 (4)
C3—C7—N8—C9	−177.1 (2)	C14—C13—C15—C16	41.8 (3)
C7—N8—C9—C14	−2.2 (4)	C12—C13—C15—C16	150.5 (3)
C7—N8—C9—C10	175.7 (2)	C14—C13—C15—C17	167.3 (2)
N8—C9—C10—O19	−68.9 (3)	C12—C13—C15—C17	−83.9 (3)
C14—C9—C10—O19	109.2 (3)	C14—C13—C15—C11	−82.1 (3)
N8—C9—C10—C18	47.9 (3)	C12—C13—C15—C11	26.6 (2)
C14—C9—C10—C18	−134.0 (3)	C10—C11—C15—C16	−36.4 (4)
N8—C9—C10—C11	173.4 (2)	C12—C11—C15—C16	−146.1 (3)
C14—C9—C10—C11	−8.6 (3)	C10—C11—C15—C17	−165.5 (2)
O19—C10—C11—C12	−64.8 (3)	C12—C11—C15—C17	84.8 (3)
C18—C10—C11—C12	178.9 (2)	C10—C11—C15—C13	83.1 (3)
C9—C10—C11—C12	53.6 (3)	C12—C11—C15—C13	−26.6 (2)
O19—C10—C11—C15	−160.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O19—H19···N1^i	0.84	2.02	2.855 (3)	171

Symmetry code: (i) x−1/2, −y+1/2, −z.