[Sulfonyl­bis­(bromo­methyl­ene)]di­benzene

Corfield, P.W.R.

doi:10.1107/S2414314621013511

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 1| January 2022| x211351

https://doi.org/10.1107/S2414314621013511

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[Sulfonylbis(bromomethylene)]dibenzene

Peter W. R. Corfield ^a ^*

^aDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA
^*Correspondence e-mail: pcorfield@fordham.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 November 2021; accepted 21 December 2021; online 7 January 2022)

The title compound, C₁₄H₁₂Br₂O₂S, crystallizes as the meso isomer of a diastereoisomeric pair. This structure determination was key to determining that the 1,3 elimination of bromine by triphenylphosphine occurs with inversion of the configuration at each of the two chiral carbon atoms. In the crystal, the molecules are linked by weak C—H⋯O and C—H⋯Br hydrogen bonds.

Keywords: crystal structure; diasteromer; sulfone; 1,3 elimination.

CCDC reference: 2130377

Structure description

This structure determination was undertaken because of the high interest in the stereochemistry of 1,3 elimination reactions, particularly in the formation of α-sulfonyl carbanions (Cram et al., 1966 ; Bordwell et al., 1968a ). Two diastereoisomers, 1 and 2, of PhCHBr·SO₂·CHBrPh (Fig. 1) react stereospecifically with triphenylphosphine leading to 1,3 elimination of bromine followed by loss of sulfur dioxide to give stilbene, PhCH=CHPh, with 1 giving almost exclusively trans stilbene and 2 giving cis stilbene. Determination that the title compound 2 was the meso isomer was key to showing that the elimination occurred with double inversion of chirality at the C atoms (Bordwell et al., 1968b ).

Figure 1
The two diastereoisomers, 1 and 2, of PhCHBr·SO₂·CHBrPh.

Bond lengths and angles in the molecular structure of 2 appear normal. As can be seen in Fig. 2, the chirality at C1 is R while that at C9 is S, indicating that this compound is the meso isomer. All molecules in this centrosymmetric crystal will be the same meso isomer, although of course half will have opposite chiralities at C1 and C9. The C1—Br1 entity is gauche with respect to S—C2, whereas C2—Br2 is trans to S—C1, with conformational angles of −58.3 (5) and 171.3 (4)°, respectively.

Figure 2
View of the title molecule showing the atomic numbering and displacement ellipsoids at the 50% probability level.

The packing diagram (Fig. 3) shows the sulfone O atoms and the Br atoms projecting into hydrophobic areas of the crystal. A number of putative C—H⋯O and C—H⋯Br intermolecular hydrogen-bonding contacts are given in Table 1. The C⋯O distances range from 3.46 (2) to 3.55 (2) Å while angles at the H atom are in the general range of 120–130°. The three C⋯Br distances listed are longer, with a range of 3.74 (2) to 3.79 (2) Å and there is more variation in the angles at the H atoms. Intermolecular H⋯H contacts are all greater than 2.5 Å except for H6⋯H10(x − $[{1\over 2}]$ , y, $[{3\over 2}]$ − z), which is 2.36 Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	0.93	2.92	3.523 (14)	123
C7—H7⋯O1ⁱ	0.93	2.80	3.462 (13)	129
C11—H11⋯O1ⁱⁱ	0.93	2.92	3.486 (14)	120
C12—H12⋯O2ⁱⁱⁱ	0.93	2.89	3.545 (15)	128
C14—H14⋯O1^iv	0.93	2.86	3.539 (17)	131
C14—H14⋯O2^iv	0.93	2.86	3.548 (14)	132
C7—H7⋯Br1^v	0.93	3.18	3.777 (14)	124
C8—H8⋯Br2ⁱⁱ	0.93	2.88	3.789 (15)	166
C13—H13⋯Br2^iv	0.93	3.12	3.741 (19)	126
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) .

Figure 3
Projection of the crystal structure of 2 down the b axis. An arbitrary sphere size is given for C and H atoms, and a 50% probability level for the displacement ellipsoids of Br, S and O atoms. The reference molecule has Br and S atoms identified.

Synthesis and crystallization

Details of the synthesis of the title compound are not given in the Bordwell papers, but details of two methods of preparing the compound are given in Carpino et al. (1971 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₂Br₂O₂S
M_r	404.12
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	295
a, b, c (Å)	16.53 (10), 12.81 (5), 13.46 (7)
V (Å³)	2850 (25)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	5.83
Crystal size (mm)	0.60 × 0.50 × 0.40

Data collection
Diffractometer	Picker, punched card control
Absorption correction	Empirical (using intensity measurements) four-dimensional tensor analysis (Parkin et al., 1995)
T_min, T_max	0.148, 0.226
No. of measured, independent and observed [I > 2σ(I)] reflections	1334, 1334, 1059
R_int	0
θ_max (°)	20.0
(sin θ/λ)_max (Å⁻¹)	0.482

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.105, 1.10
No. of reflections	1334
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.42
Computer programs: PICK (local program by J. A. Ibers), PICKOUT (local program by R. J. Doedens), FORDAP (local version), SHELXL (Sheldrick, 2015 ), ORTEP-III (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 2012 ), and publCIF (Westrip, 2010 ).

In 1967, when this dataset was collected, mechanical failures were frequent enough that minimum redundancy was sought. This accounts for the low resolution of the data and the lack of symmetry-equivalents. An empirical absorption correction involving a 24-parameter fit was made with XABS2 (Parkin et al., 1995 ), which led to a much smoother difference-Fourier map. The H atoms attached to chiral C1 and C2 atoms were located as the two highest peaks on a difference map calculated without their contributions.

In the final refinements, the phenyl ring carbon atoms were refined as rigid groups in order to keep a reasonable ratio of observations to refined parameters. The C—C distance in the phenyl rings was set at 1.372 Å to minimize the weighted R factor. Although this distance is a little less than the average 1.39 Å usually found, a number of well-refined sulfone structures in the Cambridge Structural Database (Groom et al., 2016 ) have C—C distances less than 1.39 Å, see: TUXFIC02 (Eccles et al., 2011 ), BECRAE (Malwal & Chakrapani, 2015 ), GIPQON (Periasamy et al., 2013 ), HEXLOO (Matsumoto et al., 2018 ). The phenyl and H atoms attached to chiral C atoms all were constrained to lie in their expected positions, with C—H distances of 0.93 and 0.98 Å respectively, and displacement parameters set at 1.2U_eq for the adjoining carbon atoms.

Structural data

CCDC reference: 2130377

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621013511/wm4157sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621013511/wm4157Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314621013511/wm4157Isup3.cml

checkCIF report

Computing details top

Data collection: PICK (local program by J. A. Ibers); cell refinement: PICK (local program by J. A. Ibers); data reduction: PICKOUT (local program by R. J. Doedens); program(s) used to solve structure: FORDAP (local version); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: ORTEP-III (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

[Sulfonylbis(bromomethylene)]dibenzene top

Crystal data top

C₁₄H₁₂Br₂O₂S	D_x = 1.884 Mg m⁻³ D_m = 1.86 (1) Mg m⁻³ D_m measured by flotation in CH₃I/CCl₄
M_r = 404.12	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, Pbca	Cell parameters from 10 reflections
a = 16.53 (10) Å	θ = 3.1–16.1°
b = 12.81 (5) Å	µ = 5.83 mm⁻¹
c = 13.46 (7) Å	T = 295 K
V = 2850 (25) Å³	Block, colorless
Z = 8	0.60 × 0.50 × 0.40 mm
F(000) = 1584

Data collection top

Picker, punched card control diffractometer	R_int = 0
Radiation source: sealed X-ray tube	θ_max = 20.0°, θ_min = 2.5°
θ/2θ scans	h = 0→15
Absorption correction: empirical (using intensity measurements) four-dimensional tensor analysis (Parkin et al., 1995)	k = 0→12
T_min = 0.148, T_max = 0.226	l = 0→12
1334 measured reflections	3 standard reflections every 200 reflections
1334 independent reflections	intensity decay: 0(1)
1059 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: mixed
wR(F²) = 0.105	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
1334 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

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. After the empirical absorption correction with XABS2, a difference map based upon all of the atoms except H1 and H2 clearly revealed H1 and H2 as the two highest peaks.

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

	x	y	z	U_iso*/U_eq
Br1	0.53460 (5)	0.75393 (8)	0.42515 (7)	0.0479 (4)
Br2	0.81089 (6)	0.86936 (8)	0.53831 (8)	0.0592 (4)
S	0.66395 (13)	0.74518 (19)	0.58854 (17)	0.0397 (7)
O1	0.6327 (4)	0.8427 (5)	0.6245 (5)	0.0514 (18)
O2	0.7024 (4)	0.6746 (5)	0.6565 (4)	0.0522 (18)
C1	0.5828 (5)	0.6707 (6)	0.5315 (6)	0.035 (2)
H1	0.605758	0.607183	0.502400	0.042*
C2	0.7319 (5)	0.7715 (6)	0.4857 (6)	0.039 (2)
H2	0.701115	0.807103	0.433486	0.047*
C3	0.5219 (3)	0.6398 (5)	0.6091 (4)	0.034 (2)
C4	0.4714 (4)	0.7116 (4)	0.6524 (5)	0.046 (3)
H4	0.474013	0.781339	0.633557	0.055*
C5	0.4171 (4)	0.6804 (6)	0.7235 (5)	0.055 (3)
H5	0.382825	0.729053	0.752842	0.066*
C6	0.4132 (3)	0.5774 (7)	0.7513 (4)	0.062 (3)
H6	0.376382	0.556327	0.799451	0.074*
C7	0.4637 (4)	0.5057 (4)	0.7079 (5)	0.062 (3)
H7	0.461127	0.435885	0.726776	0.075*
C8	0.5181 (4)	0.5368 (5)	0.6369 (5)	0.048 (3)
H8	0.552316	0.488169	0.607490	0.058*
C9	0.7698 (4)	0.6757 (4)	0.4412 (5)	0.044 (3)
C10	0.8307 (4)	0.6217 (5)	0.4877 (4)	0.041 (2)
H10	0.848985	0.643029	0.549794	0.050*
C11	0.8646 (3)	0.5363 (5)	0.4425 (6)	0.059 (3)
H11	0.905920	0.499671	0.473964	0.071*
C12	0.8377 (4)	0.5049 (4)	0.3508 (6)	0.057 (3)
H12	0.860697	0.446934	0.320211	0.069*
C13	0.7768 (4)	0.5589 (6)	0.3044 (4)	0.054 (3)
H13	0.758539	0.537555	0.242287	0.064*
C14	0.7429 (3)	0.6443 (5)	0.3496 (5)	0.043 (3)
H14	0.701603	0.680914	0.318116	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0465 (6)	0.0488 (7)	0.0482 (6)	−0.0038 (5)	−0.0090 (5)	0.0088 (5)
Br2	0.0507 (7)	0.0452 (7)	0.0817 (8)	−0.0152 (5)	−0.0008 (6)	−0.0116 (6)
S	0.0405 (14)	0.0389 (15)	0.0397 (15)	−0.0038 (13)	−0.0045 (12)	−0.0029 (13)
O1	0.056 (4)	0.043 (4)	0.055 (4)	0.001 (3)	0.000 (3)	−0.018 (4)
O2	0.049 (4)	0.066 (4)	0.042 (4)	0.005 (4)	−0.010 (3)	0.014 (4)
C1	0.032 (5)	0.027 (5)	0.046 (6)	0.002 (4)	0.005 (5)	−0.001 (5)
C2	0.040 (6)	0.042 (7)	0.035 (5)	−0.009 (5)	−0.007 (5)	0.011 (5)
C3	0.040 (6)	0.024 (6)	0.038 (6)	0.000 (5)	−0.004 (5)	−0.005 (5)
C4	0.047 (7)	0.050 (7)	0.041 (6)	0.006 (6)	−0.001 (5)	0.006 (5)
C5	0.049 (7)	0.057 (8)	0.058 (8)	0.010 (6)	0.001 (6)	−0.016 (6)
C6	0.056 (8)	0.086 (9)	0.043 (6)	−0.019 (7)	0.004 (6)	−0.014 (7)
C7	0.080 (8)	0.037 (7)	0.070 (8)	−0.015 (7)	0.011 (6)	0.006 (6)
C8	0.058 (8)	0.035 (7)	0.052 (7)	0.000 (5)	0.014 (6)	−0.011 (5)
C9	0.043 (6)	0.031 (6)	0.056 (8)	−0.005 (5)	0.003 (5)	0.015 (6)
C10	0.049 (7)	0.039 (6)	0.036 (6)	0.003 (5)	0.007 (5)	0.006 (6)
C11	0.067 (8)	0.037 (7)	0.073 (9)	0.004 (6)	−0.004 (7)	0.002 (6)
C12	0.068 (8)	0.034 (6)	0.069 (9)	−0.007 (6)	0.027 (6)	−0.005 (6)
C13	0.063 (8)	0.053 (8)	0.046 (7)	−0.011 (6)	0.006 (6)	−0.004 (6)
C14	0.049 (6)	0.034 (7)	0.047 (7)	−0.002 (5)	−0.009 (6)	0.008 (5)

Geometric parameters (Å, º) top

Br1—C1	1.954 (10)	C6—C7	1.3720
Br2—C2	1.943 (10)	C6—H6	0.9300
S—O2	1.435 (7)	C7—C8	1.3720
S—O1	1.436 (7)	C7—H7	0.9300
S—C1	1.817 (10)	C8—H8	0.9300
S—C2	1.815 (11)	C9—C10	1.3720
C1—C3	1.503 (11)	C9—C14	1.3720
C1—H1	0.9800	C10—C11	1.3720
C2—C9	1.502 (10)	C10—H10	0.9300
C2—H2	0.9800	C11—C12	1.3720
C3—C4	1.3720	C11—H11	0.9300
C3—C8	1.3720	C12—C13	1.3720
C4—C5	1.3720	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.3720
C5—C6	1.3720	C13—H13	0.9300
C5—H5	0.9300	C14—H14	0.9300

O2—S—O1	119.5 (5)	C7—C6—C5	120.0
O2—S—C1	105.4 (5)	C7—C6—H6	120.0
O1—S—C1	109.5 (5)	C5—C6—H6	120.0
O2—S—C2	109.2 (5)	C6—C7—C8	120.0
O1—S—C2	108.5 (4)	C6—C7—H7	120.0
C1—S—C2	103.4 (5)	C8—C7—H7	120.0
C3—C1—S	109.8 (7)	C7—C8—C3	120.0
C3—C1—Br1	112.4 (6)	C7—C8—H8	120.0
S—C1—Br1	108.9 (5)	C3—C8—H8	120.0
C3—C1—H1	108.6	C10—C9—C14	120.0
S—C1—H1	108.6	C10—C9—C2	122.4 (6)
Br1—C1—H1	108.6	C14—C9—C2	117.5 (6)
C9—C2—S	114.2 (5)	C11—C10—C9	120.0
C9—C2—Br2	113.1 (6)	C11—C10—H10	120.0
S—C2—Br2	104.9 (5)	C9—C10—H10	120.0
C9—C2—H2	108.1	C10—C11—C12	120.0
S—C2—H2	108.1	C10—C11—H11	120.0
Br2—C2—H2	108.1	C12—C11—H11	120.0
C4—C3—C8	120.0	C13—C12—C11	120.0
C4—C3—C1	121.7 (6)	C13—C12—H12	120.0
C8—C3—C1	118.3 (6)	C11—C12—H12	120.0
C5—C4—C3	120.0	C12—C13—C14	120.0
C5—C4—H4	120.0	C12—C13—H13	120.0
C3—C4—H4	120.0	C14—C13—H13	120.0
C4—C5—C6	120.0	C13—C14—C9	120.0
C4—C5—H5	120.0	C13—C14—H14	120.0
C6—C5—H5	120.0	C9—C14—H14	120.0

O2—S—C1—C3	63.6 (6)	C3—C4—C5—C6	0.0
O1—S—C1—C3	−66.2 (6)	C4—C5—C6—C7	0.0
C2—S—C1—C3	178.3 (5)	C5—C6—C7—C8	0.0
O2—S—C1—Br1	−172.9 (4)	C6—C7—C8—C3	0.0
O1—S—C1—Br1	57.3 (5)	C4—C3—C8—C7	0.0
C2—S—C1—Br1	−58.3 (5)	C1—C3—C8—C7	179.5 (6)
O2—S—C2—C9	47.6 (7)	S—C2—C9—C10	−74.4 (7)
O1—S—C2—C9	179.5 (6)	Br2—C2—C9—C10	45.5 (7)
C1—S—C2—C9	−64.3 (7)	S—C2—C9—C14	107.3 (6)
O2—S—C2—Br2	−76.8 (6)	Br2—C2—C9—C14	−132.8 (4)
O1—S—C2—Br2	55.1 (5)	C14—C9—C10—C11	0.0
C1—S—C2—Br2	171.3 (4)	C2—C9—C10—C11	−178.2 (6)
S—C1—C3—C4	71.0 (6)	C9—C10—C11—C12	0.0
Br1—C1—C3—C4	−50.4 (7)	C10—C11—C12—C13	0.0
S—C1—C3—C8	−108.5 (5)	C11—C12—C13—C14	0.0
Br1—C1—C3—C8	130.1 (4)	C12—C13—C14—C9	0.0
C8—C3—C4—C5	0.0	C10—C9—C14—C13	0.0
C1—C3—C4—C5	−179.5 (6)	C2—C9—C14—C13	178.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.92	3.523 (14)	123
C7—H7···O1ⁱ	0.93	2.80	3.462 (13)	129
C11—H11···O1ⁱⁱ	0.93	2.92	3.486 (14)	120
C12—H12···O2ⁱⁱⁱ	0.93	2.89	3.545 (15)	128
C14—H14···O1^iv	0.93	2.86	3.539 (17)	131
C14—H14···O2^iv	0.93	2.86	3.548 (14)	132
C7—H7···Br1^v	0.93	3.18	3.777 (14)	124
C8—H8···Br2ⁱⁱ	0.93	2.88	3.789 (15)	166
C13—H13···Br2^iv	0.93	3.12	3.741 (19)	126

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+3/2, y−1/2, z; (iii) −x+3/2, −y+1, z−1/2; (iv) x, −y+3/2, z−1/2; (v) −x+1, −y+1, −z+1.

Acknowledgements

The author gratefully acknowledges the permission of J. A. Ibers to use the Picker diffractometer at Northwestern University.

References

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