(+)-(1R,2S,3S,4S)-2-Chloro-3-(phenyl­selan­yl)cyclo­hexane-1,4-diol

The cyclo­hexyl ring in the title compound, C₁₂H₁₅ClO₂Se, has a chair conformation with the 4-hydr­oxy group occupying an axial position; the other non-H substituents occupy equatorial positions. Mol­ecules aggregate via O—H...O hydrogen bonds into a supra­molecular helical chain.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.077
• Data-to-parameter ratio = 19.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.60

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.595
            Tmax scaled      0.595 Tmin scaled      0.510
PLAT793_ALERT_1_G Check the Absolute Configuration of C1     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C4     = ...          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 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
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

Recently, we reported the application of epoxidation and dihydroxylation to the olefinic portion of 1,2-dioxines, giving modified 1,2-dioxines, which were subsequently converted into novel epoxy hydroxy ketones, and sugar-type derivatives (Greatrex et al., 2003; Robinson et al., 2006). In the course of investigating other useful electrophilic additions, we attempted addition of phenylselenenyl chloride across the alkene of the bicyclic peroxide 2,3-dioxa-bicyclo[2.2.2]oct-7-ene. Such additions have been well documented on other alkene bearing organic compounds (Engman, 1989; Toshimitsu et al., 1981, 1985), generally giving trans-1,2-phenylselenyl chloro adducts (Ho & Kolt, 1982; Clive et al., 1977), or in the presence of other nucleophiles, such as water or methanol, phenylselenenly alkoxide adducts can be formed (Nicolaou et al., 1979; Tiecco et al., 1988). Interestingly, addition of phenylselenenyl chloride to the peroxide was accompanied by simultaneous reduction of the peroxide bond to give the cyclohexyl-1,4-diol, (I). Also, even though the reaction was performed in methanol, no displacement of the halogen was observed.

The molecular structure of (I) (Fig. 1) shows the cyclohexyl ring to adopt a chair conformation with the Se, Cl, O1 and O4 substituents occupying equatorial, equatorial, equatorial, and axial positions, respectively. The Se—C_phenyl bond is shorter than the Se—C_methine bond and the geometry about the Se atom is bent (Table 1). Molecules aggregate in the crystal structure via O—H···O hydrogen bonds to form a supramolecular chain (Table 2). The chain is propagated by the screw axis and thus has a helical topology (Fig. 2). Interactions between chains are of the type π···π. Phenyl substituents are interdigitated along the b axis; the Cg···Cg distance is 3.7545 (14) Å for symmetry operation -x, -y, -z. However, as seen from Fig. 3, the aromatic rings overlap only partially with the closest approach involving the C31 and C33 atoms at 3.369 (3) Å.

Related literature

For related literature, see: Clive et al. (1977); Engman (1989); Greatrex et al. (2003); Ho & Kolt (1982); Nicolaou et al. (1979); Robinson et al. (2006); Tiecco et al. (1988); Toshimitsu et al. (1981, 1985).

S2. Experimental

To a stirred solution of 2,3-dioxa-bicyclo[2.2.2]oct-7-ene (100 mg, 0.9 mmol) in anhydrous methanol (5 ml) was added phenylselenenyl chloride (205 mg, 1.08 mmol) and the solution stirred under an atmosphere of N₂ until reaction was complete, by TLC (ca 16 h). The reaction mixture was then diluted with dichloromethane (50 ml), washed with sat. sodium bicarbonate solution (2 x 25 ml), followed by brine (20 ml) and dried (Na₂SO₄). The solvent was removed in vacuo, and the residue purified by flash chromatography to give (I) as a white solid. The pure material was recrystallized from a slowly evaporating mixture of 1:1 dichloromethane/heptane to give colourless prisms (204 mg, 75%); m.p. 381–382 K. R_f 0.26 (2:3 ethyl acetate/hexane). Elemental analysis found: C 47.15, H, 4.95%; C₁₂H₁₅ClO₂Se requires: C 47.26, H, 5.02%. IR (nujol) 3297, 1581, 1506, 1330, 1046, 1000 cm^{-1. 1}H NMR (600 MHz, CDCl₃): δ 1.49–1.55 (m, 1H), 1.87–1.95 (m, 2H), 2.05 (dddd, J = 3.6, 3.6, 7.8, 14.4 Hz, 1H), 2.46 (br s, 2H), 3.44 (dd, J = 2.4, 11.4 Hz, 1H), 3.65 (ddd, J = 6.3, 9.0, 10.2 Hz, 1H), 3.85 (ddd, J = 2.4, 2.4, 3.6 Hz, 1H), 4.13 (dd, J = 9.0, 11.4 Hz, 1H), 7.29–7.36 (m, 3H), 7.63–7.66 (m, 2H). ¹³C NMR (150 MHz, CDCl₃): δ 25.7, 28.6, 56.9, 66.1, 66.1, 75.4, 127.6, 128.5, 129.5, 137.2. MS m/z (+EI): 308 (M⁺, ³⁷Cl, 23), 306 (M⁺, ³⁵Cl, 52), 158 (100), 131 (31), 113 (24), 77 (61), 67 (84).

S3. Refinement

All H atoms were included in the riding-model approximation, with C—H = 0.94 to 0.99 Å and O—H = 0.83 Å, and with U_iso(H) = 1.2U_eq(C) and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. View of the supramolecular chain in (I) mediated by hydrogen bonds, shown as orange-dashed lines. Colour code: yellow (selenium), cyan (chloride), red (oxygen), grey (carbon) and green (hydrogen).
	Fig. 3. View of the unit-cell contents of (I) down the b axis. Hydrogen bonding (O—H···O) contacts are shown as orange-dashed lines.

(+)-(1R,2S,3S,4S)-2-Chloro-3-(phenylselanyl)cyclohexane-1,4-diol

Crystal data

C12H15ClO2Se	F(000) = 616
Mr = 305.65	Dx = 1.649 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 2654 reflections
a = 13.5529 (10) Å	θ = 2.3–29.0°
b = 7.0627 (5) Å	µ = 3.25 mm^−1
c = 12.9203 (9) Å	T = 223 K
β = 95.443 (1)°	Block, colourless
V = 1231.16 (15) Å^3	0.47 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2832 independent reflections
Radiation source: fine-focus sealed tube	2524 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→17
Tmin = 0.857, Tmax = 1	k = −9→7
8348 measured reflections	l = −14→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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0442P)^2 + 0.3384P] where P = (Fo^2 + 2Fc^2)/3
2832 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.31 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
Se3	0.223073 (15)	0.05198 (3)	0.126906 (17)	0.02977 (9)
Cl2	0.26790 (4)	0.52886 (7)	0.17758 (4)	0.03242 (13)
O1	0.44699 (11)	0.57891 (19)	0.33447 (12)	0.0285 (3)
H1	0.4960	0.5419	0.3061	0.043*
O4	0.40103 (11)	−0.05964 (19)	0.26849 (13)	0.0302 (3)
H4	0.4139	−0.1691	0.2890	0.045*
C1	0.38350 (15)	0.4218 (3)	0.34966 (16)	0.0247 (4)
H1A	0.3289	0.4669	0.3891	0.030*
C2	0.33780 (14)	0.3428 (3)	0.24551 (15)	0.0220 (4)
H2	0.3920	0.3041	0.2038	0.026*
C3	0.27180 (14)	0.1719 (3)	0.25939 (15)	0.0232 (4)
H3	0.2138	0.2144	0.2944	0.028*
C4	0.32598 (15)	0.0194 (3)	0.32663 (17)	0.0264 (4)
H4A	0.2783	−0.0814	0.3407	0.032*
C5	0.37069 (17)	0.1005 (3)	0.42939 (17)	0.0314 (4)
H5A	0.4083	0.0014	0.4689	0.038*
H5B	0.3173	0.1422	0.4702	0.038*
C6	0.43905 (16)	0.2672 (3)	0.41313 (16)	0.0296 (4)
H6A	0.4651	0.3184	0.4808	0.035*
H6B	0.4952	0.2238	0.3769	0.035*
C31	0.09343 (14)	0.1616 (3)	0.10249 (16)	0.0270 (4)
C32	0.06268 (16)	0.2203 (3)	0.00253 (17)	0.0319 (5)
H32	0.1073	0.2192	−0.0489	0.038*
C33	−0.03398 (17)	0.2810 (3)	−0.02180 (18)	0.0372 (5)
H33	−0.0550	0.3189	−0.0901	0.045*
C34	−0.09930 (17)	0.2861 (3)	0.05327 (19)	0.0374 (5)
H34	−0.1647	0.3281	0.0366	0.045*
C35	−0.06820 (17)	0.2291 (4)	0.15351 (19)	0.0412 (6)
H35	−0.1124	0.2341	0.2053	0.049*
C36	0.02774 (17)	0.1648 (4)	0.17807 (18)	0.0371 (5)
H36	0.0481	0.1234	0.2459	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Se3	0.02667 (13)	0.02833 (14)	0.03375 (14)	0.00167 (8)	−0.00011 (9)	−0.00736 (8)
Cl2	0.0381 (3)	0.0241 (3)	0.0338 (3)	0.0085 (2)	−0.0032 (2)	0.0045 (2)
O1	0.0286 (7)	0.0197 (7)	0.0374 (8)	−0.0010 (6)	0.0037 (6)	−0.0028 (6)
O4	0.0291 (8)	0.0170 (7)	0.0455 (9)	0.0032 (5)	0.0093 (7)	0.0031 (6)
C1	0.0271 (10)	0.0206 (9)	0.0263 (10)	0.0002 (7)	0.0022 (8)	0.0000 (7)
C2	0.0227 (9)	0.0176 (9)	0.0256 (9)	0.0036 (7)	0.0020 (7)	0.0014 (7)
C3	0.0213 (8)	0.0217 (9)	0.0265 (9)	0.0001 (7)	0.0024 (7)	−0.0015 (7)
C4	0.0245 (9)	0.0214 (9)	0.0338 (11)	−0.0019 (8)	0.0056 (8)	0.0041 (8)
C5	0.0364 (11)	0.0289 (10)	0.0284 (11)	0.0004 (9)	0.0008 (9)	0.0084 (9)
C6	0.0336 (11)	0.0267 (10)	0.0267 (10)	−0.0010 (8)	−0.0061 (8)	0.0018 (8)
C31	0.0237 (9)	0.0242 (10)	0.0326 (10)	−0.0014 (8)	−0.0005 (8)	−0.0034 (8)
C32	0.0332 (11)	0.0314 (11)	0.0311 (11)	−0.0013 (9)	0.0025 (9)	0.0006 (9)
C33	0.0372 (12)	0.0383 (12)	0.0343 (12)	−0.0014 (10)	−0.0068 (10)	0.0013 (10)
C34	0.0286 (10)	0.0386 (13)	0.0436 (13)	0.0046 (9)	−0.0041 (9)	−0.0071 (10)
C35	0.0312 (11)	0.0530 (15)	0.0401 (13)	0.0021 (11)	0.0066 (10)	−0.0037 (11)
C36	0.0332 (11)	0.0472 (14)	0.0305 (11)	0.0009 (10)	0.0004 (9)	0.0007 (10)

Geometric parameters (Å, º)

Se3—C3	1.9669 (19)	C5—C6	1.525 (3)
Se3—C31	1.919 (2)	C5—H5A	0.9800
C2—Cl2	1.7990 (19)	C5—H5B	0.9800
C1—O1	1.429 (2)	C6—H6A	0.9800
O1—H1	0.8300	C6—H6B	0.9800
C4—O4	1.434 (3)	C31—C32	1.383 (3)
O4—H4	0.8300	C31—C36	1.383 (3)
C1—C6	1.521 (3)	C32—C33	1.386 (3)
C1—C2	1.532 (3)	C32—H32	0.9400
C1—H1A	0.9900	C33—C34	1.374 (3)
C2—C3	1.523 (3)	C33—H33	0.9400
C2—H2	0.9900	C34—C35	1.383 (3)
C3—C4	1.527 (3)	C34—H34	0.9400
C3—H3	0.9900	C35—C36	1.386 (3)
C4—C5	1.518 (3)	C35—H35	0.9400
C4—H4A	0.9900	C36—H36	0.9400
C3—Se3—C31	101.31 (8)	C6—C5—H5A	109.3
C1—O1—H1	109.5	C4—C5—H5B	109.3
C4—O4—H4	109.5	C6—C5—H5B	109.3
O1—C1—C6	110.96 (16)	H5A—C5—H5B	108.0
O1—C1—C2	111.13 (16)	C1—C6—C5	110.63 (17)
C6—C1—C2	110.52 (16)	C1—C6—H6A	109.5
O1—C1—H1A	108.0	C5—C6—H6A	109.5
C6—C1—H1A	108.0	C1—C6—H6B	109.5
C2—C1—H1A	108.0	C5—C6—H6B	109.5
C3—C2—C1	112.21 (16)	H6A—C6—H6B	108.1
C3—C2—Cl2	110.39 (13)	C32—C31—C36	119.85 (19)
C1—C2—Cl2	108.25 (13)	C32—C31—Se3	117.70 (16)
C3—C2—H2	108.6	C36—C31—Se3	122.11 (16)
C1—C2—H2	108.6	C31—C32—C33	119.9 (2)
Cl2—C2—H2	108.6	C31—C32—H32	120.0
C2—C3—C4	111.71 (15)	C33—C32—H32	120.0
C2—C3—Se3	113.03 (13)	C34—C33—C32	120.4 (2)
C4—C3—Se3	107.17 (13)	C34—C33—H33	119.8
C2—C3—H3	108.3	C32—C33—H33	119.8
C4—C3—H3	108.3	C33—C34—C35	119.6 (2)
Se3—C3—H3	108.3	C33—C34—H34	120.2
O4—C4—C5	111.15 (17)	C35—C34—H34	120.2
O4—C4—C3	107.65 (16)	C36—C35—C34	120.4 (2)
C5—C4—C3	111.23 (17)	C36—C35—H35	119.8
O4—C4—H4A	108.9	C34—C35—H35	119.8
C5—C4—H4A	108.9	C35—C36—C31	119.8 (2)
C3—C4—H4A	108.9	C35—C36—H36	120.1
C4—C5—C6	111.59 (17)	C31—C36—H36	120.1
C4—C5—H5A	109.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4^i	0.83	1.91	2.737 (2)	174
O4—H4···O1^ii	0.83	1.91	2.744 (2)	178

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