The rel-R,R-enanti­omer of 7-[7-hydroxybi­cyclo[4.2.0]octa-1(6),2,4-trien-7-yl]bi­cyclo­[4.2.0]octa-1(6),2,4-trien-7-ol

Detert, H.; Schollmeyer, D.

doi:10.1107/S241431461801550X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 11| November 2018| x181550

https://doi.org/10.1107/S241431461801550X

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The rel-R,R-enantiomer of 7-[7-hydroxybicyclo[4.2.0]octa-1(6),2,4-trien-7-yl]bicyclo[4.2.0]octa-1(6),2,4-trien-7-ol

Heiner Detert ^a ^* and Dieter Schollmeyer ^a

^aUniversity of Mainz, Institut of Organic Chemistry, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 25 October 2018; accepted 2 November 2018; online 9 November 2018)

A single crystal of the rel-R,R-enantiomer of the title compound, C₁₆H₁₄O₂, was analyzed. The molecular structure is characterized by nearly planar cyclobutene rings and a torsion angle of the diol unit of 68.3 (2)°. Strands parallel to the b axis are built from diols connected via hydrogen bonds.

Keywords: crystal structure; cyclobutene; pinacole; hydrogen bonds.

CCDC reference: 1876786

Structure description

A single-crystal of the isomeric mixture of the title compound (Fig. 1) was analysed, consisting of the pure rel-R,R-enantiomer. The bond lengths of the benzocyclobutene fragments are typical for this unit, both four-membered rings are planar, the sums of bond angles are 359.96° and 359.45° resp. The bond angles at the sp²-carbons are 93.1 (2)° (C9—C16—C11), 93.8 (2)° (C10—C11—C16), 94.3 (2)° (C8—C3—C2), and 93.2 (2)° (C3—C8—C1).

Figure 1
Perspective view of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

The dihedral angle between the best planes of the cyclobutane units is 58.5 (2)° and the central torsion angle of the glycol subunit is 68.2 (3)°. In the crystal, the molecules (symmetry transformed by a a twofold screw axis) form strands along the b-axis direction. Hydrogen bonds (Fig. 2, Table 1) parallel to the b-axis [O1—H1⋯O2, 1.92 (4) Å, 170 (3)°] connect molecules with translational symmetry, hydrogen bonds in direction of the c-axis [O2—H2⋯O1, 1.91 (4) Å, 152.0 (4)°] connect two molecules which are symmetry-related by the screw axis.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.87 (4)	1.92 (4)	2.782 (3)	170 (3)
O2—H2⋯O1ⁱⁱ	0.94 (4)	1.91 (4)	2.782 (3)	152 (4)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Figure 2
Partial packing diagram, view along the a axis. Hydrogen bonds are drawn with dashed lines.

Synthesis and crystallization

The reductive coupling of aldehydes or ketones with low-valent titanium (McMurry, 1989 ) is an important route to stilbenes (Meier, 1992 ), even to stilbenes with severe geometrical strain (Lenoir, 1989 ; Dobryakov et al., 2016 ). The reaction proceeds via a pinacol intermediate, the geometry of which is decisive for the configuration of the product. The McMurry reaction of benzocyclobutenone (Schiess & Heitzmann, 1977 ) results in a mixture of E– and Z-di(benzocyclobutylidene) (Schneider et al., 1999 ) together with a pinacol (40%) of unknown geometry (Oelgemöller et al., 2002 ). H NMR spectroscopy of the crude product mixture showed a 6:4 ratio of the stilbene (ca 1:1 mixture of both isomers) and the diol. A single crystal from the mixture of the diols was investigated.

H NMR (400 MHz; CDCl₃): δH = 1.53 (2 H, br s, OH), 3.04 (2 H, d, J = 14.4, 2-H), 3.17 (2 H, br s, 1-H), 3.30 (2 H, d, J = 14.4, 2-H), 7.01–7.18 (8 H, br m, H_arom); C NMR (100 MHz; CDCl₃) δC = 42.7 (t, 2 × C-2), 82.9 (d, 2 × C-1), 121.4 (d, 2 × C_arom), 123.2 (d, 2 × C_arom), 127.1 (d, 2 × C_arom), 129.5 (d, 2 × C_arom), 142.3 (s, 2 × C_arom) and 146.8 (s, 2 × C_arom). Recrystallization from chloroform/propanol-2 (v/v = 1:3) yielded colourless crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The absolute configuration could not be determined and was arbitrarily set.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₄O₂
M_r	238.27
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	193
a, b, c (Å)	10.1497 (12), 5.1276 (4), 11.6896 (16)
β (°)	99.541 (10)
V (Å³)	599.95 (12)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.13 × 0.07

Data collection
Diffractometer	Stoe IPDS 2T
No. of measured, independent and observed [I > 2σ(I)] reflections	4954, 2964, 2371
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.097, 1.05
No. of reflections	2964
No. of parameters	171
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.18
Absolute structure	Flack x determined using 875 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	1.6 (10)
Computer programs: X-AREA and X-RED (Stoe & Cie, 1996 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2017 (Sheldrick, 2015b ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1876786

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S241431461801550X/bt4076sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461801550X/bt4076Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461801550X/bt4076Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 1996); cell refinement: X-AREA (Stoe & Cie, 1996); data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015b).

7-[7-Hydroxybicyclo[4.2.0]octa-1(6),2,4-trien-7-yl]bicyclo[4.2.0]octa-1(6),2,4-trien-7-ol top

Crystal data top

C₁₆H₁₄O₂	F(000) = 252
M_r = 238.27	D_x = 1.319 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 10.1497 (12) Å	Cell parameters from 4652 reflections
b = 5.1276 (4) Å	θ = 2.0–28.5°
c = 11.6896 (16) Å	µ = 0.09 mm⁻¹
β = 99.541 (10)°	T = 193 K
V = 599.95 (12) Å³	Needle, colourless
Z = 2	0.50 × 0.13 × 0.07 mm

Data collection top

Stoe IPDS 2T diffractometer	2371 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	R_int = 0.032
Detector resolution: 6.67 pixels mm^-1	θ_max = 28.4°, θ_min = 2.0°
rotation method scans	h = −13→13
4954 measured reflections	k = −6→6
2964 independent reflections	l = −14→15

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.031P)² + 0.2519P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.24 e Å⁻³
2964 reflections	Δρ_min = −0.17 e Å⁻³
171 parameters	Absolute structure: Flack x determined using 875 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 1.6 (10)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Hydroxyl hydrogen atoms were localized in difference fourier maps and freely refined.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.51056 (18)	0.2981 (4)	0.41147 (15)	0.0237 (4)
H1	0.471 (3)	0.154 (8)	0.385 (3)	0.044 (10)*
O2	0.40202 (18)	0.8096 (4)	0.35005 (17)	0.0249 (4)
H2	0.421 (4)	0.750 (8)	0.427 (4)	0.061 (12)*
C1	0.5454 (3)	0.4489 (5)	0.3182 (2)	0.0212 (5)
C2	0.6155 (3)	0.2889 (6)	0.2297 (2)	0.0253 (6)
H2A	0.627109	0.101101	0.248340	0.030*
H2B	0.576281	0.316258	0.147268	0.030*
C3	0.7381 (3)	0.4546 (5)	0.2718 (2)	0.0253 (6)
C4	0.8688 (3)	0.4972 (6)	0.2584 (3)	0.0352 (7)
H4	0.909902	0.401865	0.204145	0.042*
C5	0.9363 (3)	0.6876 (7)	0.3290 (3)	0.0387 (8)
H5	1.026509	0.725004	0.322585	0.046*
C6	0.8763 (3)	0.8265 (7)	0.4093 (3)	0.0369 (7)
H6	0.926413	0.955950	0.455706	0.044*
C7	0.7447 (3)	0.7799 (6)	0.4230 (2)	0.0289 (6)
H7	0.703271	0.872062	0.477908	0.035*
C8	0.6785 (3)	0.5907 (5)	0.3514 (2)	0.0225 (6)
C9	0.4249 (3)	0.6156 (5)	0.2679 (2)	0.0206 (5)
C10	0.4233 (3)	0.7324 (5)	0.1430 (2)	0.0247 (6)
H10A	0.394867	0.917068	0.134744	0.030*
H10B	0.506586	0.702490	0.111143	0.030*
C11	0.3129 (3)	0.5373 (5)	0.1021 (2)	0.0246 (6)
C12	0.2315 (3)	0.4363 (6)	0.0055 (3)	0.0321 (7)
H12	0.237744	0.491510	−0.070953	0.038*
C13	0.1395 (3)	0.2481 (6)	0.0277 (3)	0.0327 (7)
H13	0.081726	0.172058	−0.035734	0.039*
C14	0.1298 (3)	0.1684 (6)	0.1395 (3)	0.0289 (6)
H14	0.064511	0.042157	0.150384	0.035*
C15	0.2132 (2)	0.2686 (5)	0.2363 (2)	0.0253 (6)
H15	0.207527	0.213816	0.312948	0.030*
C16	0.3047 (3)	0.4528 (5)	0.2133 (2)	0.0227 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0308 (10)	0.0192 (9)	0.0210 (9)	−0.0022 (9)	0.0038 (7)	0.0016 (8)
O2	0.0318 (10)	0.0181 (9)	0.0245 (10)	0.0027 (9)	0.0040 (8)	−0.0024 (8)
C1	0.0246 (13)	0.0176 (12)	0.0217 (13)	−0.0008 (11)	0.0051 (10)	0.0004 (11)
C2	0.0323 (14)	0.0225 (13)	0.0213 (12)	0.0031 (13)	0.0047 (10)	−0.0012 (12)
C3	0.0280 (14)	0.0239 (13)	0.0239 (14)	0.0040 (12)	0.0039 (11)	0.0061 (12)
C4	0.0309 (15)	0.0411 (18)	0.0357 (17)	0.0050 (14)	0.0111 (13)	0.0094 (14)
C5	0.0263 (14)	0.0472 (19)	0.0417 (18)	−0.0035 (14)	0.0028 (13)	0.0137 (16)
C6	0.0313 (15)	0.0356 (16)	0.0395 (17)	−0.0075 (15)	−0.0068 (13)	0.0077 (15)
C7	0.0294 (14)	0.0255 (14)	0.0294 (14)	−0.0023 (13)	−0.0020 (11)	0.0007 (13)
C8	0.0232 (13)	0.0202 (13)	0.0236 (13)	0.0024 (11)	0.0020 (11)	0.0045 (11)
C9	0.0230 (13)	0.0171 (12)	0.0213 (13)	0.0005 (10)	0.0030 (10)	0.0001 (10)
C10	0.0280 (13)	0.0217 (14)	0.0241 (13)	0.0000 (11)	0.0035 (11)	0.0039 (11)
C11	0.0235 (13)	0.0227 (14)	0.0268 (14)	0.0024 (11)	0.0022 (11)	0.0007 (11)
C12	0.0334 (16)	0.0367 (16)	0.0246 (14)	0.0015 (14)	0.0004 (12)	0.0019 (13)
C13	0.0271 (14)	0.0370 (18)	0.0308 (15)	−0.0011 (13)	−0.0050 (12)	−0.0093 (14)
C14	0.0214 (13)	0.0277 (15)	0.0370 (17)	−0.0024 (12)	0.0027 (12)	−0.0020 (12)
C15	0.0235 (12)	0.0246 (14)	0.0277 (13)	0.0027 (12)	0.0044 (10)	0.0025 (12)
C16	0.0226 (12)	0.0208 (13)	0.0244 (13)	0.0019 (11)	0.0029 (10)	−0.0012 (11)

Geometric parameters (Å, º) top

O1—C1	1.429 (3)	C7—C8	1.380 (4)
O1—H1	0.87 (4)	C7—H7	0.9500
O2—C9	1.428 (3)	C9—C16	1.527 (4)
O2—H2	0.94 (4)	C9—C10	1.576 (4)
C1—C8	1.527 (4)	C10—C11	1.519 (4)
C1—C9	1.528 (3)	C10—H10A	0.9900
C1—C2	1.579 (4)	C10—H10B	0.9900
C2—C3	1.519 (4)	C11—C12	1.384 (4)
C2—H2A	0.9900	C11—C16	1.386 (4)
C2—H2B	0.9900	C12—C13	1.397 (4)
C3—C4	1.379 (4)	C12—H12	0.9500
C3—C8	1.380 (4)	C13—C14	1.388 (4)
C4—C5	1.385 (5)	C13—H13	0.9500
C4—H4	0.9500	C14—C15	1.393 (4)
C5—C6	1.397 (5)	C14—H14	0.9500
C5—H5	0.9500	C15—C16	1.382 (4)
C6—C7	1.391 (4)	C15—H15	0.9500
C6—H6	0.9500

C1—O1—H1	110 (2)	C7—C8—C1	144.2 (3)
C9—O2—H2	113 (2)	O2—C9—C16	117.0 (2)
O1—C1—C8	112.6 (2)	O2—C9—C1	109.9 (2)
O1—C1—C9	108.2 (2)	C16—C9—C1	112.82 (19)
C8—C1—C9	116.7 (2)	O2—C9—C10	112.4 (2)
O1—C1—C2	114.5 (2)	C16—C9—C10	86.32 (19)
C8—C1—C2	86.47 (19)	C1—C9—C10	117.0 (2)
C9—C1—C2	117.3 (2)	C11—C10—C9	86.26 (19)
C3—C2—C1	86.04 (19)	C11—C10—H10A	114.3
C3—C2—H2A	114.3	C9—C10—H10A	114.3
C1—C2—H2A	114.3	C11—C10—H10B	114.3
C3—C2—H2B	114.3	C9—C10—H10B	114.3
C1—C2—H2B	114.3	H10A—C10—H10B	111.4
H2A—C2—H2B	111.5	C12—C11—C16	121.8 (3)
C4—C3—C8	122.3 (3)	C12—C11—C10	144.3 (3)
C4—C3—C2	143.4 (3)	C16—C11—C10	93.8 (2)
C8—C3—C2	94.3 (2)	C11—C12—C13	115.7 (3)
C3—C4—C5	115.7 (3)	C11—C12—H12	122.1
C3—C4—H4	122.1	C13—C12—H12	122.1
C5—C4—H4	122.1	C14—C13—C12	122.2 (3)
C4—C5—C6	122.1 (3)	C14—C13—H13	118.9
C4—C5—H5	118.9	C12—C13—H13	118.9
C6—C5—H5	118.9	C13—C14—C15	121.8 (3)
C7—C6—C5	121.6 (3)	C13—C14—H14	119.1
C7—C6—H6	119.2	C15—C14—H14	119.1
C5—C6—H6	119.2	C16—C15—C14	115.6 (3)
C8—C7—C6	115.6 (3)	C16—C15—H15	122.2
C8—C7—H7	122.2	C14—C15—H15	122.2
C6—C7—H7	122.2	C15—C16—C11	122.9 (3)
C3—C8—C7	122.7 (3)	C15—C16—C9	143.9 (3)
C3—C8—C1	93.2 (2)	C11—C16—C9	93.1 (2)

O1—C1—C2—C3	−114.5 (2)	C2—C1—C9—C16	67.0 (3)
C8—C1—C2—C3	−1.30 (18)	O1—C1—C9—C10	−162.1 (2)
C9—C1—C2—C3	117.1 (2)	C8—C1—C9—C10	69.7 (3)
C1—C2—C3—C4	179.5 (4)	C2—C1—C9—C10	−30.8 (3)
C1—C2—C3—C8	1.4 (2)	O2—C9—C10—C11	−122.9 (2)
C8—C3—C4—C5	−0.7 (4)	C16—C9—C10—C11	−5.15 (19)
C2—C3—C4—C5	−178.4 (3)	C1—C9—C10—C11	108.6 (2)
C3—C4—C5—C6	0.4 (5)	C9—C10—C11—C12	−174.8 (4)
C4—C5—C6—C7	0.2 (5)	C9—C10—C11—C16	5.7 (2)
C5—C6—C7—C8	−0.7 (4)	C16—C11—C12—C13	1.1 (4)
C4—C3—C8—C7	0.3 (4)	C10—C11—C12—C13	−178.3 (4)
C2—C3—C8—C7	179.0 (3)	C11—C12—C13—C14	0.4 (4)
C4—C3—C8—C1	179.9 (3)	C12—C13—C14—C15	−1.2 (5)
C2—C3—C8—C1	−1.5 (2)	C13—C14—C15—C16	0.5 (4)
C6—C7—C8—C3	0.4 (4)	C14—C15—C16—C11	1.0 (4)
C6—C7—C8—C1	−178.9 (3)	C14—C15—C16—C9	−172.8 (3)
O1—C1—C8—C3	116.5 (2)	C12—C11—C16—C15	−1.8 (4)
C9—C1—C8—C3	−117.4 (2)	C10—C11—C16—C15	177.8 (3)
C2—C1—C8—C3	1.4 (2)	C12—C11—C16—C9	174.5 (3)
O1—C1—C8—C7	−64.1 (5)	C10—C11—C16—C9	−5.9 (2)
C9—C1—C8—C7	61.9 (5)	O2—C9—C16—C15	−66.3 (5)
C2—C1—C8—C7	−179.2 (4)	C1—C9—C16—C15	62.7 (5)
O1—C1—C9—O2	68.3 (2)	C10—C9—C16—C15	−179.6 (4)
C8—C1—C9—O2	−59.9 (3)	O2—C9—C16—C11	118.9 (2)
C2—C1—C9—O2	−160.4 (2)	C1—C9—C16—C11	−112.1 (2)
O1—C1—C9—C16	−64.3 (3)	C10—C9—C16—C11	5.6 (2)
C8—C1—C9—C16	167.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.87 (4)	1.92 (4)	2.782 (3)	170 (3)
O2—H2···O1ⁱⁱ	0.94 (4)	1.91 (4)	2.782 (3)	152 (4)

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

Acknowledgements

The authors are grateful to Professor Dr D. Lenoir for a sample of benzocyclobutenone.

References

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