(1R,2R)-2-(2-Bromo­phenoxy)-1,2-di­hydro­naphthalen-1-ol

The regio-, relative, and absolute stereochemistry of the title compound, C₁₆H₁₃BrO₂, have been established. Molecules are linked by intermolecular O—H...O hydrogen bonds [H...O 2.00 (6) Å and O—H...O 168 (7)°] through 2₁ screw axes to form chains in the a-axis direction.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.039
• wR factor = 0.085
• Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               2317
         Count of symmetry unique reflns         1396
         Completeness (_total/calc)            165.97%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       921
         Fraction of Friedel pairs measured     0.660
         Are heavy atom types Z>Si present          yes
          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.

---

S1. Comment

Recently, we reported a new rhodium-catalysed ring-opening reaction of 1,4-dihydro-1,4-epoxynaphthalene with a wide range of phenols (Lautens et al., 2000). The 1,2-regio-, trans and relative stereochemistry, as well as the absolute stereochemistry, for the addition of 2-bomophenol were established by X-ray diffraction analysis when (R)-(-)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi-tert-butylphosphine [(R)-(S)-PPF-PtBu₂] is used as the chiral ligand.

Molecules of the title compound, (I), are linked through 2₁ screw axes to form intermolecular hydrogen-bonded chains parallel to the a axis (Fig. 2 and Table 2). In the dihydronaphthalene group, an analysis (Cremer & Pople, 1975) of the puckering in the six-membered ring (C1/C2/C3/C8/C9/C10) gives Q_T = 0.466 (4) Å. The conformation analysis of that ring (Duax et al., 1976) shows that the conformation is a half-chair, with a local pseudo-twofold axis running along the midpoints of the C1—C2 and C8—C9 bonds.

S2. Experimental

The title compound was obtained as a white crystalline solid in 90% yield and 97% enantiomeric excess by treatment of 1,4-dihydro-1,4-epoxynaphthalene in refluxing tetrahydrofuran with 4-bromophenol and a catalyst prepared from [Rh(cyclooctadiene)Cl]₂, (R)-(S)-PPF-PtBu₂, silver trifluoromethanesulfonate and tetrabutylammonium iodide (Lautens & Fagnou, 2001). Suitable enantiomerically pure crystals were grown from pentane.

S3. Refinement

With the exception of the hydroxyl H atom, all H atoms were included in calculated positions, with C—H distances of 0.95 and 1.00 Å, and then included in the refinement in riding-motion approximation, with U_iso = 1.2U_eq of the carrier atom. The hydroxyl H atom was refined independently with an isotropic displacement parameter. 921 Friedel pairs were used to determine the absolute stereochemistry.

Computing details

Data collection: COLLECT (Nonius, 1997-2001); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2001); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. View of (I), showing the crystallographic labelling scheme. Ellipsoids are at the 50% probability level.
	Fig. 2. View of the hydrogen-bonding mode along the a axis in (I).

(1R,2R)-2-(2-Bromophenoxy)-1,2-dihydronaphthalen-1-ol

Crystal data

C16H13BrO2	F(000) = 640
Mr = 317.17	Dx = 1.622 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1370 reflections
a = 4.6070 (2) Å	θ = 2.5–25.0°
b = 11.2898 (4) Å	µ = 3.16 mm^−1
c = 24.9751 (12) Å	T = 150 K
V = 1299.01 (10) Å^3	Needle, colourless
Z = 4	0.35 × 0.08 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer	2317 independent reflections
Radiation source: fine-focus sealed tube	1897 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
Detector resolution: 9 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ϕ scans, and ω scans with κ offsets	h = −5→5
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	k = −13→13
Tmin = 0.404, Tmax = 0.786	l = −29→29
6770 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0189P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.085	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.38 e Å^−3
2317 reflections	Δρmin = −0.40 e Å^−3
177 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0039 (10)
Primary atom site location: structure-invariant direct methods	Absolute structure: (Flack, 1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.015 (16)

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
Br1	1.10408 (12)	0.14084 (4)	0.275845 (19)	0.03464 (18)
O1	0.8052 (7)	0.2060 (2)	0.38147 (11)	0.0269 (8)
O2	0.6098 (9)	0.3053 (3)	0.48223 (12)	0.0270 (7)
H1O	0.746 (14)	0.267 (6)	0.489 (2)	0.06 (2)*
C1	0.5733 (11)	0.2928 (3)	0.38473 (16)	0.0224 (10)
H1A	0.3836	0.2510	0.3895	0.027*
C2	0.6308 (10)	0.3715 (3)	0.43340 (14)	0.0205 (9)
H2A	0.8319	0.4042	0.4305	0.025*
C3	0.4200 (11)	0.4731 (3)	0.43445 (16)	0.0204 (9)
C4	0.3122 (10)	0.5197 (4)	0.48182 (17)	0.0244 (11)
H4A	0.3720	0.4872	0.5151	0.029*
C5	0.1160 (12)	0.6143 (3)	0.48096 (18)	0.0307 (11)
H5A	0.0410	0.6447	0.5136	0.037*
C6	0.0313 (11)	0.6634 (4)	0.43303 (19)	0.0312 (12)
H6A	−0.1006	0.7281	0.4325	0.037*
C7	0.1398 (11)	0.6180 (3)	0.38528 (17)	0.0288 (11)
H7A	0.0809	0.6521	0.3523	0.035*
C8	0.3337 (10)	0.5231 (3)	0.38509 (16)	0.0221 (11)
C9	0.4462 (11)	0.4736 (4)	0.33534 (17)	0.0295 (12)
H9A	0.4360	0.5186	0.3033	0.035*
C10	0.5626 (11)	0.3664 (4)	0.33454 (16)	0.0274 (11)
H10A	0.6399	0.3357	0.3021	0.033*
C12	0.7255 (11)	0.0944 (4)	0.36361 (18)	0.0269 (11)
C13	0.5233 (11)	0.0274 (4)	0.39235 (18)	0.0314 (13)
H13A	0.4347	0.0589	0.4236	0.038*
C14	0.4533 (13)	−0.0857 (4)	0.37470 (19)	0.0360 (14)
H14A	0.3111	−0.1304	0.3934	0.043*
C15	0.5885 (13)	−0.1341 (4)	0.33018 (19)	0.0373 (12)
H15A	0.5455	−0.2129	0.3194	0.045*
C16	0.7862 (11)	−0.0671 (4)	0.30154 (19)	0.0333 (13)
H16A	0.8773	−0.0994	0.2707	0.040*
C17	0.8513 (12)	0.0475 (3)	0.31804 (16)	0.0275 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0337 (3)	0.0385 (3)	0.0318 (3)	0.0004 (3)	0.0032 (3)	−0.0005 (2)
O1	0.024 (2)	0.0253 (16)	0.0318 (17)	0.0014 (14)	−0.0010 (16)	−0.0055 (13)
O2	0.0236 (19)	0.0350 (17)	0.0223 (16)	0.0048 (18)	0.0030 (18)	0.0076 (13)
C1	0.018 (3)	0.023 (2)	0.026 (2)	0.001 (2)	0.001 (2)	−0.0014 (18)
C2	0.021 (2)	0.021 (2)	0.019 (2)	0.000 (2)	0.000 (2)	0.0031 (17)
C3	0.020 (3)	0.018 (2)	0.024 (2)	−0.002 (2)	0.005 (2)	0.0019 (17)
C4	0.025 (3)	0.025 (2)	0.022 (2)	−0.005 (2)	−0.002 (2)	−0.0006 (18)
C5	0.034 (3)	0.026 (2)	0.032 (3)	0.000 (2)	0.002 (3)	−0.0064 (18)
C6	0.033 (3)	0.024 (2)	0.037 (3)	0.003 (2)	0.002 (2)	0.001 (2)
C7	0.030 (3)	0.023 (2)	0.033 (3)	−0.009 (2)	−0.002 (3)	0.0049 (18)
C8	0.026 (3)	0.018 (2)	0.023 (2)	−0.007 (2)	−0.002 (2)	0.0030 (17)
C9	0.031 (3)	0.034 (3)	0.023 (2)	−0.004 (2)	−0.002 (2)	0.0029 (19)
C10	0.036 (3)	0.027 (2)	0.020 (2)	0.001 (3)	−0.001 (2)	−0.0017 (19)
C12	0.030 (3)	0.025 (2)	0.026 (3)	−0.002 (2)	−0.007 (2)	−0.0019 (19)
C13	0.041 (4)	0.028 (3)	0.025 (3)	−0.003 (2)	−0.005 (2)	0.001 (2)
C14	0.039 (4)	0.028 (3)	0.041 (3)	−0.005 (3)	−0.012 (3)	0.011 (2)
C15	0.046 (3)	0.023 (2)	0.043 (3)	0.002 (3)	−0.012 (3)	−0.003 (2)
C16	0.035 (3)	0.035 (3)	0.030 (3)	0.008 (2)	−0.007 (3)	−0.005 (2)
C17	0.029 (3)	0.027 (2)	0.026 (2)	0.004 (2)	−0.002 (2)	0.0017 (18)

Geometric parameters (Å, º)

Br1—C17	1.892 (5)	C6—H6A	0.9500
O1—C12	1.386 (5)	C7—C8	1.395 (6)
O1—C1	1.452 (5)	C7—H7A	0.9500
O2—C2	1.433 (5)	C8—C9	1.458 (6)
O2—H1O	0.78 (6)	C9—C10	1.324 (6)
C1—C10	1.504 (6)	C9—H9A	0.9500
C1—C2	1.528 (5)	C10—H10A	0.9500
C1—H1A	1.0000	C12—C17	1.383 (6)
C2—C3	1.504 (6)	C12—C13	1.398 (6)
C2—H2A	1.0000	C13—C14	1.388 (6)
C3—C4	1.387 (6)	C13—H13A	0.9500
C3—C8	1.413 (6)	C14—C15	1.387 (7)
C4—C5	1.399 (6)	C14—H14A	0.9500
C4—H4A	0.9500	C15—C16	1.383 (7)
C5—C6	1.376 (6)	C15—H15A	0.9500
C5—H5A	0.9500	C16—C17	1.391 (6)
C6—C7	1.391 (6)	C16—H16A	0.9500
C12—O1—C1	115.9 (4)	C8—C7—H7A	119.5
C2—O2—H1O	114 (5)	C7—C8—C3	118.9 (4)
O1—C1—C10	110.5 (4)	C7—C8—C9	121.7 (4)
O1—C1—C2	108.0 (4)	C3—C8—C9	119.4 (4)
C10—C1—C2	110.3 (3)	C10—C9—C8	120.5 (4)
O1—C1—H1A	109.3	C10—C9—H9A	119.8
C10—C1—H1A	109.3	C8—C9—H9A	119.8
C2—C1—H1A	109.3	C9—C10—C1	120.4 (4)
O2—C2—C3	109.8 (3)	C9—C10—H10A	119.8
O2—C2—C1	111.2 (3)	C1—C10—H10A	119.8
C3—C2—C1	110.2 (4)	C17—C12—O1	120.1 (4)
O2—C2—H2A	108.5	C17—C12—C13	119.6 (4)
C3—C2—H2A	108.5	O1—C12—C13	120.2 (4)
C1—C2—H2A	108.5	C14—C13—C12	119.3 (5)
C4—C3—C8	119.5 (4)	C14—C13—H13A	120.4
C4—C3—C2	122.4 (4)	C12—C13—H13A	120.4
C8—C3—C2	118.1 (4)	C15—C14—C13	120.9 (5)
C3—C4—C5	120.5 (4)	C15—C14—H14A	119.6
C3—C4—H4A	119.7	C13—C14—H14A	119.6
C5—C4—H4A	119.7	C16—C15—C14	119.6 (5)
C6—C5—C4	120.3 (4)	C16—C15—H15A	120.2
C6—C5—H5A	119.9	C14—C15—H15A	120.2
C4—C5—H5A	119.9	C15—C16—C17	119.8 (5)
C5—C6—C7	119.7 (4)	C15—C16—H16A	120.1
C5—C6—H6A	120.2	C17—C16—H16A	120.1
C7—C6—H6A	120.2	C12—C17—C16	120.7 (4)
C6—C7—C8	121.1 (4)	C12—C17—Br1	120.2 (3)
C6—C7—H7A	119.5	C16—C17—Br1	119.1 (4)
C12—O1—C1—C10	−94.9 (4)	C2—C3—C8—C9	1.1 (6)
C12—O1—C1—C2	144.3 (4)	C7—C8—C9—C10	−161.4 (5)
O1—C1—C2—O2	−65.6 (5)	C3—C8—C9—C10	17.9 (7)
C10—C1—C2—O2	173.6 (4)	C8—C9—C10—C1	1.6 (7)
O1—C1—C2—C3	172.4 (3)	O1—C1—C10—C9	−156.1 (4)
C10—C1—C2—C3	51.5 (5)	C2—C1—C10—C9	−36.8 (6)
O2—C2—C3—C4	22.5 (6)	C1—O1—C12—C17	120.4 (5)
C1—C2—C3—C4	145.3 (4)	C1—O1—C12—C13	−61.3 (5)
O2—C2—C3—C8	−158.4 (4)	C17—C12—C13—C14	0.3 (7)
C1—C2—C3—C8	−35.5 (5)	O1—C12—C13—C14	−178.0 (4)
C8—C3—C4—C5	1.0 (7)	C12—C13—C14—C15	2.2 (7)
C2—C3—C4—C5	−179.9 (4)	C13—C14—C15—C16	−2.9 (8)
C3—C4—C5—C6	−1.0 (7)	C14—C15—C16—C17	1.0 (7)
C4—C5—C6—C7	0.5 (7)	O1—C12—C17—C16	176.1 (4)
C5—C6—C7—C8	0.0 (7)	C13—C12—C17—C16	−2.2 (7)
C6—C7—C8—C3	−0.1 (7)	O1—C12—C17—Br1	−6.2 (6)
C6—C7—C8—C9	179.2 (4)	C13—C12—C17—Br1	175.5 (3)
C4—C3—C8—C7	−0.4 (7)	C15—C16—C17—C12	1.6 (7)
C2—C3—C8—C7	−179.6 (4)	C15—C16—C17—Br1	−176.2 (4)
C4—C3—C8—C9	−179.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O···O2^i	0.78 (6)	2.00 (6)	2.766 (3)	168 (7)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.