3,5-Dibromo-2,2,6,6,7,7-hexa­methyl­octane-4-one

Sorensen, T.S.; Hou, J.; Parvez, M.

doi:10.1107/S160053681204603X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3367

doi:10.1107/S160053681204603X

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3,5-Dibromo-2,2,6,6,7,7-hexamethyloctane-4-one

Ted S. Sorensen,^a Jianjun Hou ^a and Masood Parvez ^a ^*

^aDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
^*Correspondence e-mail: parvez@ucalgary.ca

(Received 6 November 2012; accepted 7 November 2012; online 17 November 2012)

In the title molecule, C₁₄H₂₆Br₂O, the central carbonyl group (C₃O) is essentially planar (r.m.s. deviation = 0.0021 Å). The Br atoms lie on the same side of the molecule and are approximately syn, with a Br—C⋯C—Br torsion angle of −43.52 (13)°. The crystal structure is devoid of any specific intermolecular interactions.

Related literature

For background literature and the synthesis and crystal structures of related compounds, see: Parvez et al. (2002 )

Experimental

Crystal data

C₁₄H₂₆Br₂O
M_r = 370.17
Monoclinic, P 2₁ /c
a = 14.602 (5) Å
b = 9.963 (2) Å
c = 10.974 (4) Å
β = 93.321 (13)°
V = 1593.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 5.07 mm⁻¹
T = 123 K
0.16 × 0.14 × 0.04 mm

Data collection

Nonius APEXII CCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ) T_min = 0.498, T_max = 0.823
6698 measured reflections
3630 independent reflections
3044 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.073
S = 1.06
3630 reflections
162 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681204603X/tk5169sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681204603X/tk5169Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681204603X/tk5169Isup3.cml

checkCIF report

Comment top

In continuation of our investigations on the characterization of ketones, we now report the crystal structure of the title compound (Fig. 1). The molecular dimensions in the title molecule agree very well with the corresponding molecular dimensions reported in closely related compounds (Parvez et al., 2002). The crystal structure (Fig. 2) is devoid of any intermolecular interactions.

Related literature top

For background literature and the synthesis and crystal structures of related compounds, see: Parvez et al. (2002)

Experimental top

The synthesis of the title compound and related compounds has been reported earlier (Parvez et al., 2002). Crystals suitable for crystallographic studies were grown from pentane/CH₂Cl₂ (1:1).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP drawing (Farrugia, 1997) of the title molecule with the displacement ellipsoids plotted at 50% probability level; H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the unit cell packing of the crystal structure of the title compound. H atoms were omitted for clarity.

3,5-Dibromo-2,2,6,6,7,7-hexamethyloctane-4-one top

Crystal data top

C₁₄H₂₆Br₂O	F(000) = 752
M_r = 370.17	D_x = 1.543 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6698 reflections
a = 14.602 (5) Å	θ = 3.1–27.5°
b = 9.963 (2) Å	µ = 5.07 mm⁻¹
c = 10.974 (4) Å	T = 123 K
β = 93.321 (13)°	Plate, colourless
V = 1593.8 (9) Å³	0.16 × 0.14 × 0.04 mm
Z = 4

Data collection top

Nonius APEXII CCD diffractometer	3630 independent reflections
Radiation source: fine-focus sealed tube	3044 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω and ϕ scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −18→18
T_min = 0.498, T_max = 0.823	k = −12→12
6698 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0402P)² + 0.279P] where P = (F_o² + 2F_c²)/3
3630 reflections	(Δ/σ)_max < 0.001
162 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

C₁₄H₂₆Br₂O	V = 1593.8 (9) Å³
M_r = 370.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.602 (5) Å	µ = 5.07 mm⁻¹
b = 9.963 (2) Å	T = 123 K
c = 10.974 (4) Å	0.16 × 0.14 × 0.04 mm
β = 93.321 (13)°

Data collection top

Nonius APEXII CCD diffractometer	3630 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	3044 reflections with I > 2σ(I)
T_min = 0.498, T_max = 0.823	R_int = 0.022
6698 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.06	Δρ_max = 0.49 e Å⁻³
3630 reflections	Δρ_min = −0.62 e Å⁻³
162 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.119984 (18)	0.34952 (2)	0.04616 (2)	0.02780 (9)
Br2	0.198646 (17)	0.02636 (2)	0.21493 (2)	0.02471 (9)
O1	0.32951 (12)	0.29847 (16)	0.09933 (14)	0.0265 (4)
C1	0.07327 (18)	0.6488 (2)	0.1864 (2)	0.0244 (5)
H1A	0.0159	0.6851	0.2148	0.037*
H1B	0.0595	0.5852	0.1197	0.037*
H1C	0.1108	0.7223	0.1572	0.037*
C2	0.12605 (16)	0.5761 (2)	0.29239 (18)	0.0177 (4)
C3	0.21494 (16)	0.5004 (2)	0.25226 (19)	0.0170 (4)
C4	0.19353 (16)	0.3561 (2)	0.20209 (18)	0.0171 (5)
H4	0.1584	0.3079	0.2642	0.021*
C5	0.27965 (16)	0.2724 (2)	0.18064 (18)	0.0175 (4)
C6	0.29800 (15)	0.1531 (2)	0.26737 (19)	0.0168 (4)
H6	0.2863	0.1840	0.3518	0.020*
C7	0.39337 (16)	0.0872 (2)	0.27212 (19)	0.0201 (5)
C8	0.42040 (19)	0.0297 (2)	0.1499 (2)	0.0276 (6)
H8A	0.4825	−0.0078	0.1593	0.041*
H8B	0.4189	0.1012	0.0885	0.041*
H8C	0.3771	−0.0412	0.1236	0.041*
C9	0.15287 (19)	0.6853 (2)	0.3883 (2)	0.0266 (5)
H9A	0.1732	0.6423	0.4656	0.040*
H9B	0.0996	0.7424	0.4010	0.040*
H9C	0.2028	0.7402	0.3591	0.040*
C10	0.05875 (18)	0.4806 (2)	0.3510 (2)	0.0249 (5)
H10A	0.0916	0.4279	0.4150	0.037*
H10B	0.0314	0.4200	0.2887	0.037*
H10C	0.0102	0.5329	0.3869	0.037*
C11	0.26542 (17)	0.5849 (2)	0.1600 (2)	0.0242 (5)
H11A	0.3257	0.5451	0.1483	0.036*
H11B	0.2734	0.6766	0.1910	0.036*
H11C	0.2294	0.5868	0.0818	0.036*
C12	0.28176 (18)	0.4758 (2)	0.3644 (2)	0.0227 (5)
H12A	0.3337	0.4217	0.3401	0.034*
H12B	0.2497	0.4281	0.4274	0.034*
H12C	0.3043	0.5621	0.3969	0.034*
C13	0.46246 (18)	0.1962 (2)	0.3165 (2)	0.0278 (5)
H13A	0.5239	0.1569	0.3269	0.042*
H13B	0.4446	0.2324	0.3947	0.042*
H13C	0.4627	0.2686	0.2561	0.042*
C14	0.39600 (19)	−0.0260 (2)	0.3682 (2)	0.0267 (5)
H14A	0.4584	−0.0621	0.3785	0.040*
H14B	0.3537	−0.0977	0.3409	0.040*
H14C	0.3776	0.0099	0.4463	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03166 (17)	0.02673 (14)	0.02357 (13)	0.00707 (10)	−0.01094 (10)	−0.00763 (9)
Br2	0.02415 (15)	0.01923 (13)	0.03042 (14)	−0.00386 (9)	−0.00116 (10)	−0.00072 (8)
O1	0.0318 (11)	0.0245 (8)	0.0242 (8)	0.0076 (7)	0.0108 (7)	0.0059 (6)
C1	0.0284 (15)	0.0209 (11)	0.0237 (11)	0.0097 (9)	−0.0002 (10)	0.0027 (8)
C2	0.0207 (13)	0.0153 (10)	0.0173 (10)	0.0038 (9)	0.0027 (9)	0.0006 (8)
C3	0.0171 (12)	0.0170 (10)	0.0166 (10)	0.0004 (9)	−0.0012 (9)	−0.0004 (8)
C4	0.0176 (12)	0.0196 (11)	0.0139 (10)	0.0016 (8)	−0.0008 (9)	−0.0009 (8)
C5	0.0212 (12)	0.0155 (10)	0.0156 (10)	0.0008 (9)	−0.0011 (9)	−0.0022 (8)
C6	0.0165 (12)	0.0183 (11)	0.0157 (10)	0.0015 (8)	0.0016 (8)	0.0003 (7)
C7	0.0213 (13)	0.0191 (11)	0.0197 (10)	0.0036 (9)	0.0010 (9)	0.0004 (8)
C8	0.0312 (15)	0.0285 (13)	0.0234 (12)	0.0100 (11)	0.0048 (10)	0.0019 (9)
C9	0.0354 (16)	0.0222 (12)	0.0221 (11)	0.0069 (10)	0.0016 (10)	−0.0052 (9)
C10	0.0238 (14)	0.0220 (11)	0.0300 (12)	0.0027 (10)	0.0097 (10)	0.0047 (9)
C11	0.0244 (14)	0.0227 (12)	0.0260 (12)	−0.0034 (10)	0.0053 (10)	0.0014 (9)
C12	0.0227 (13)	0.0232 (12)	0.0216 (11)	0.0023 (9)	−0.0035 (9)	−0.0042 (8)
C13	0.0182 (13)	0.0286 (13)	0.0362 (13)	0.0009 (10)	−0.0017 (11)	0.0003 (10)
C14	0.0327 (16)	0.0246 (12)	0.0229 (12)	0.0075 (10)	0.0020 (10)	0.0042 (9)

Geometric parameters (Å, º) top

Br1—C4	1.968 (2)	C8—H8A	0.9800
Br2—C6	1.984 (2)	C8—H8B	0.9800
O1—C5	1.212 (3)	C8—H8C	0.9800
C1—C2	1.539 (3)	C9—H9A	0.9800
C1—H1A	0.9800	C9—H9B	0.9800
C1—H1B	0.9800	C9—H9C	0.9800
C1—H1C	0.9800	C10—H10A	0.9800
C2—C10	1.536 (3)	C10—H10B	0.9800
C2—C9	1.548 (3)	C10—H10C	0.9800
C2—C3	1.585 (3)	C11—H11A	0.9800
C3—C11	1.537 (3)	C11—H11B	0.9800
C3—C12	1.545 (3)	C11—H11C	0.9800
C3—C4	1.565 (3)	C12—H12A	0.9800
C4—C5	1.538 (3)	C12—H12B	0.9800
C4—H4	1.0000	C12—H12C	0.9800
C5—C6	1.536 (3)	C13—H13A	0.9800
C6—C7	1.538 (3)	C13—H13B	0.9800
C6—H6	1.0000	C13—H13C	0.9800
C7—C8	1.531 (3)	C14—H14A	0.9800
C7—C13	1.542 (3)	C14—H14B	0.9800
C7—C14	1.543 (3)	C14—H14C	0.9800

C2—C1—H1A	109.5	H8A—C8—H8B	109.5
C2—C1—H1B	109.5	C7—C8—H8C	109.5
H1A—C1—H1B	109.5	H8A—C8—H8C	109.5
C2—C1—H1C	109.5	H8B—C8—H8C	109.5
H1A—C1—H1C	109.5	C2—C9—H9A	109.5
H1B—C1—H1C	109.5	C2—C9—H9B	109.5
C10—C2—C1	107.7 (2)	H9A—C9—H9B	109.5
C10—C2—C9	107.05 (18)	C2—C9—H9C	109.5
C1—C2—C9	106.23 (18)	H9A—C9—H9C	109.5
C10—C2—C3	112.07 (17)	H9B—C9—H9C	109.5
C1—C2—C3	113.33 (17)	C2—C10—H10A	109.5
C9—C2—C3	110.13 (19)	C2—C10—H10B	109.5
C11—C3—C12	107.85 (19)	H10A—C10—H10B	109.5
C11—C3—C4	111.40 (17)	C2—C10—H10C	109.5
C12—C3—C4	103.79 (17)	H10A—C10—H10C	109.5
C11—C3—C2	110.76 (18)	H10B—C10—H10C	109.5
C12—C3—C2	110.09 (17)	C3—C11—H11A	109.5
C4—C3—C2	112.63 (18)	C3—C11—H11B	109.5
C5—C4—C3	113.79 (18)	H11A—C11—H11B	109.5
C5—C4—Br1	105.00 (13)	C3—C11—H11C	109.5
C3—C4—Br1	115.10 (14)	H11A—C11—H11C	109.5
C5—C4—H4	107.5	H11B—C11—H11C	109.5
C3—C4—H4	107.5	C3—C12—H12A	109.5
Br1—C4—H4	107.5	C3—C12—H12B	109.5
O1—C5—C6	122.1 (2)	H12A—C12—H12B	109.5
O1—C5—C4	121.87 (19)	C3—C12—H12C	109.5
C6—C5—C4	116.05 (17)	H12A—C12—H12C	109.5
C5—C6—C7	118.46 (18)	H12B—C12—H12C	109.5
C5—C6—Br2	102.39 (14)	C7—C13—H13A	109.5
C7—C6—Br2	112.55 (14)	C7—C13—H13B	109.5
C5—C6—H6	107.6	H13A—C13—H13B	109.5
C7—C6—H6	107.6	C7—C13—H13C	109.5
Br2—C6—H6	107.6	H13A—C13—H13C	109.5
C8—C7—C6	114.14 (19)	H13B—C13—H13C	109.5
C8—C7—C13	110.1 (2)	C7—C14—H14A	109.5
C6—C7—C13	106.53 (18)	C7—C14—H14B	109.5
C8—C7—C14	109.12 (18)	H14A—C14—H14B	109.5
C6—C7—C14	108.79 (19)	C7—C14—H14C	109.5
C13—C7—C14	108.0 (2)	H14A—C14—H14C	109.5
C7—C8—H8A	109.5	H14B—C14—H14C	109.5
C7—C8—H8B	109.5

C10—C2—C3—C11	162.2 (2)	C3—C4—C5—O1	−69.9 (3)
C1—C2—C3—C11	40.0 (3)	Br1—C4—C5—O1	56.8 (2)
C9—C2—C3—C11	−78.8 (2)	C3—C4—C5—C6	110.8 (2)
C10—C2—C3—C12	−78.7 (2)	Br1—C4—C5—C6	−122.49 (16)
C1—C2—C3—C12	159.22 (19)	O1—C5—C6—C7	15.5 (3)
C9—C2—C3—C12	40.4 (2)	C4—C5—C6—C7	−165.23 (18)
C10—C2—C3—C4	36.7 (2)	O1—C5—C6—Br2	−109.0 (2)
C1—C2—C3—C4	−85.5 (2)	C4—C5—C6—Br2	70.32 (19)
C9—C2—C3—C4	155.70 (17)	C5—C6—C7—C8	−59.8 (3)
C11—C3—C4—C5	63.6 (2)	Br2—C6—C7—C8	59.5 (2)
C12—C3—C4—C5	−52.2 (2)	C5—C6—C7—C13	61.9 (2)
C2—C3—C4—C5	−171.27 (17)	Br2—C6—C7—C13	−178.84 (14)
C11—C3—C4—Br1	−57.7 (2)	C5—C6—C7—C14	178.07 (18)
C12—C3—C4—Br1	−173.47 (14)	Br2—C6—C7—C14	−62.6 (2)
C2—C3—C4—Br1	67.5 (2)

Experimental details

Crystal data
Chemical formula	C₁₄H₂₆Br₂O
M_r	370.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	14.602 (5), 9.963 (2), 10.974 (4)
β (°)	93.321 (13)
V (Å³)	1593.8 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.07
Crystal size (mm)	0.16 × 0.14 × 0.04

Data collection
Diffractometer	Nonius APEXII CCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.498, 0.823
No. of measured, independent and observed [I > 2σ(I)] reflections	6698, 3630, 3044
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.06
No. of reflections	3630
No. of parameters	162
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.62

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

References

Blessing, R. H. (1997). J. Appl. Cryst. 30, 421–426. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hooft, R. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Parvez, M., Kabir, S. M. H., Sorensen, T. S., Sun, F. & Watson, B. (2002). Can. J. Chem. 80, 413–417. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar