1,3-Bis(4-bromo­phen­yl)propane

Peloquin, A.J.; Godman, N.P.; Allison, B.D.; Balaich, G.J.; Iacono, S.T.

doi:10.1107/S2414314618005631

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 4| April 2018| x180563

https://doi.org/10.1107/S2414314618005631

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1,3-Bis(4-bromophenyl)propane

Andrew J. Peloquin,^a Nicholas P. Godman,^b Bruce D. Allison,^c Gary J. Balaich ^a and Scott T. Iacono ^a ^*

^aDepartment of Chemistry & Chemistry Research Center, United States Air Force Academy, USAF Academy, Colorado 80840, USA, ^bAir Force Research Laboratory, Materials and Manufacturing Directorate, Wright-Patterson Air Force Base, Dayton, OH 45433-7750, USA, and ^cRose-Hulman Institute of Technology, 5500 Wabach Ave, Terre Haute, IN 47803, USA
^*Correspondence e-mail: scott.iacono@usafa.edu

Edited by R. J. Butcher, Howard University, USA (Received 23 March 2018; accepted 10 April 2018; online 17 April 2018)

The title compound, C₁₅H₁₄Br₂, obtained through the reduction of 4,4′-dibromochalcone, has monoclinic P2₁ symmetry at 100 K. No directional interactions could be identified in the crystal.

Keywords: crystal structure; 4-bromophenyl; propane.

CCDC reference: 1836177

Structure description

The title compound (Fig. 1) crystallizes in the monoclinic space group P2₁ with one molecule per asymmetric unit. The 4-bromophenyl substituents are located in the anti positions of the propane linker, with C4—C1—C2—C3 and C1—C2—C3–C10 torsion angles of −174.5 (3) and 179.5 (3)°, respectively. The phenyl rings are oriented in a nearly perpendicular arrangement to the propane chain as shown by the dihedral angles between the C1–C2–C3 plane and the phenyl rings of 74.7 (3)° (C4–C9) and 87.6 (3)° (C10–C15).

Figure 1
The molecular structure of 1,3-bis(4-bromophenyl)propane. Displacement ellipsoids are shown at the 50% probability level.

Despite the presence of multiple aromatic rings within the molecule, there are no obvious π-stacking interactions due to the kinked arrangement of the propane linker. The only interactions present are typical van der Waals interactions.

A search in the Cambridge Structural Database (CSD, Version 5.38, last update November 2016; Groom et al., 2016 ) revealed that a structurally similar 1,3-bis(4-bromophenyl)acetone has been reported (Varughese & Draper, 2010 )

Synthesis and crystallization

The title compound was prepared via a modified literature procedure (Murata et al., 2004 ). Triethylsilane (14.1 ml, 87.4 mmol) was added dropwise to a stirring suspension of 1,3-bis(4-bromophenyl)-2-propen-1-one (7.99 g, 21.9 mmol) in trifluoroacetic acid (20 ml) under N₂ at 0°C. The reaction mixture was stirred and slowly warmed to room temperature over 18 h. The resulting white precipitate was filtered, taken up in dichloromethane (50 ml), dried over anhydrous MgSO₄, filtered, and residual solvent was removed in vacuo. The crude, oily product solidified upon standing over 48 h. The waxy solid was recrystallized by dissolving in boiling hexanes (25 ml) and cooling (5°C). Vacuum filtration, washing with cold hexanes (10 ml), and removal of residual solvent in vacuo afforded the title compound as a pale yellow solid (4.57 g, 59.1%). Crystals suitable for single-crystal X-ray diffraction were obtained from the slow evaporation of methanol. ¹H NMR (500 MHz, CDCl₃): δ 7.41 (d, 4H, J = 8.0 Hz), 7.05 (d, 4H, J = 8.0 Hz), 2.59 (t, 4H, J = 7.5 Hz), 1.91 (p, 2H, J = 8.0 Hz). ¹³C NMR (500 MHz, CDCl₃): δ 141.0, 131.5, 130.3, 119.7, 34.8, 32.7.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₅H₁₄Br₂
M_r	354.08
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	7.4526 (13), 5.8441 (10), 16.278 (3)
β (°)	101.808 (2)
V (Å³)	694.0 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	5.82
Crystal size (mm)	0.47 × 0.25 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2017 )
T_min, T_max	0.25, 0.55
No. of measured, independent and observed [I > 2σ(I)] reflections	14936, 3562, 3421
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.055, 1.38
No. of reflections	3562
No. of parameters	154
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.35
Absolute structure	Flack x determined using 1492 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.019 (9)
Computer programs: APEX3 and SAINT (Bruker, 2017), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and SHELXL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1836177

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618005631/bv4016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618005631/bv4016Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618005631/bv4016Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL (Sheldrick, 2008).

1,3-Bis(4-bromophenyl)propane top

Crystal data top

C₁₅H₁₄Br₂	F(000) = 348
M_r = 354.08	D_x = 1.694 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.4526 (13) Å	Cell parameters from 9704 reflections
b = 5.8441 (10) Å	θ = 2.6–29.7°
c = 16.278 (3) Å	µ = 5.82 mm⁻¹
β = 101.808 (2)°	T = 100 K
V = 694.0 (2) Å³	Flat prism, clear colourless
Z = 2	0.47 × 0.25 × 0.12 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3562 independent reflections
Radiation source: fine focus sealed tube	3421 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.7°, θ_min = 2.6°
ω Scans scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −7→7
T_min = 0.25, T_max = 0.55	l = −21→21
14936 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.055	(Δ/σ)_max = 0.001
S = 1.38	Δρ_max = 0.68 e Å⁻³
3562 reflections	Δρ_min = −0.35 e Å⁻³
154 parameters	Absolute structure: Flack x determined using 1492 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.019 (9)

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. The hydrogen atoms were included in calculated positions and refined with a riding model: C–H = 0.95 and 0.98 Å for aromatic and methyl H atoms, respectively, and and U_iso(H) = 1.2 U_eq(C-aromatic) and U_iso(H) = 1.5 U_eq(C-methyl).

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

	x	y	z	U_iso*/U_eq
Br1	0.72512 (6)	0.64324 (6)	0.32150 (2)	0.02990 (11)
Br2	0.07038 (4)	0.07332 (6)	0.93844 (2)	0.01940 (9)
C1	0.7965 (5)	0.8018 (7)	0.7041 (2)	0.0203 (7)
H1A	0.773435	0.961347	0.714801	0.024*
H1B	0.91894	0.764318	0.734497	0.024*
C2	0.6578 (4)	0.6530 (7)	0.73599 (18)	0.0185 (6)
H2A	0.688304	0.493461	0.72972	0.022*
H2B	0.53722	0.679954	0.701533	0.022*
C3	0.6507 (5)	0.6981 (6)	0.8280 (2)	0.0186 (7)
H3A	0.770709	0.669457	0.862731	0.022*
H3B	0.620835	0.857725	0.834565	0.022*
C4	0.7860 (5)	0.7678 (6)	0.6108 (2)	0.0172 (7)
C5	0.6973 (5)	0.9269 (6)	0.5527 (2)	0.0194 (7)
H5	0.649793	1.05945	0.571618	0.023*
C6	0.6785 (5)	0.8907 (6)	0.4664 (2)	0.0205 (7)
H6	0.619388	0.997936	0.42798	0.025*
C7	0.7494 (5)	0.6922 (6)	0.43923 (19)	0.0191 (7)
C8	0.8384 (5)	0.5303 (6)	0.4947 (2)	0.0203 (8)
H8	0.885231	0.397812	0.475442	0.024*
C9	0.8562 (4)	0.5710 (7)	0.5808 (2)	0.0193 (6)
H9	0.916431	0.463847	0.618886	0.023*
C10	0.5111 (4)	0.5499 (6)	0.85791 (18)	0.0157 (6)
C11	0.5604 (5)	0.3371 (6)	0.8952 (2)	0.0165 (7)
H11	0.68188	0.289513	0.903494	0.02*
C12	0.4309 (4)	0.1948 (6)	0.92003 (19)	0.0162 (7)
H12	0.465409	0.054546	0.945371	0.019*
C13	0.2489 (4)	0.2666 (6)	0.90622 (19)	0.0154 (6)
C14	0.1967 (5)	0.4775 (6)	0.8701 (2)	0.0192 (7)
H14	0.075257	0.525136	0.862057	0.023*
C15	0.3282 (4)	0.6167 (6)	0.84615 (19)	0.0195 (7)
H15	0.293275	0.757895	0.821671	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0370 (2)	0.0355 (2)	0.01707 (16)	−0.00535 (17)	0.00528 (14)	−0.00373 (15)
Br2	0.01583 (15)	0.01890 (15)	0.02574 (17)	−0.00157 (13)	0.00954 (12)	0.00104 (12)
C1	0.0195 (18)	0.0252 (19)	0.0174 (15)	−0.0039 (14)	0.0069 (14)	−0.0002 (14)
C2	0.0182 (16)	0.0209 (16)	0.0183 (14)	−0.0031 (14)	0.0080 (12)	−0.0013 (14)
C3	0.0183 (17)	0.0195 (19)	0.0196 (15)	−0.0027 (14)	0.0074 (13)	−0.0016 (12)
C4	0.0133 (16)	0.0207 (17)	0.0189 (15)	−0.0030 (13)	0.0063 (13)	0.0019 (13)
C5	0.0191 (18)	0.0160 (16)	0.0243 (17)	0.0020 (13)	0.0076 (14)	0.0006 (13)
C6	0.0187 (17)	0.0202 (18)	0.0215 (17)	0.0020 (14)	0.0016 (14)	0.0052 (14)
C7	0.0194 (17)	0.0236 (19)	0.0152 (14)	−0.0042 (14)	0.0054 (12)	−0.0007 (12)
C8	0.0207 (17)	0.017 (2)	0.0266 (18)	0.0016 (13)	0.0123 (14)	−0.0007 (13)
C9	0.0185 (15)	0.0197 (16)	0.0209 (16)	0.0021 (16)	0.0069 (13)	0.0069 (15)
C10	0.0158 (14)	0.0184 (17)	0.0140 (14)	−0.0026 (13)	0.0055 (12)	−0.0041 (12)
C11	0.0135 (16)	0.0200 (17)	0.0164 (15)	0.0015 (13)	0.0045 (13)	−0.0024 (13)
C12	0.0173 (16)	0.0161 (18)	0.0159 (14)	0.0020 (13)	0.0052 (12)	0.0004 (12)
C13	0.0142 (16)	0.0189 (17)	0.0147 (14)	−0.0004 (12)	0.0070 (12)	−0.0014 (12)
C14	0.0145 (16)	0.0224 (17)	0.0218 (16)	0.0044 (14)	0.0066 (13)	0.0020 (14)
C15	0.0196 (16)	0.0171 (19)	0.0226 (15)	0.0021 (13)	0.0061 (13)	0.0035 (13)

Geometric parameters (Å, º) top

Br1—C7	1.909 (3)	C6—C7	1.384 (5)
Br2—C13	1.899 (3)	C6—H6	0.93
C1—C4	1.519 (4)	C7—C8	1.380 (5)
C1—C2	1.521 (5)	C8—C9	1.400 (5)
C1—H1A	0.97	C8—H8	0.93
C1—H1B	0.97	C9—H9	0.93
C2—C3	1.532 (4)	C10—C15	1.392 (4)
C2—H2A	0.97	C10—C11	1.400 (5)
C2—H2B	0.97	C11—C12	1.395 (5)
C3—C10	1.509 (5)	C11—H11	0.93
C3—H3A	0.97	C12—C13	1.393 (4)
C3—H3B	0.97	C12—H12	0.93
C4—C9	1.392 (5)	C13—C14	1.387 (5)
C4—C5	1.393 (5)	C14—C15	1.390 (5)
C5—C6	1.399 (5)	C14—H14	0.93
C5—H5	0.93	C15—H15	0.93

C4—C1—C2	111.5 (3)	C8—C7—C6	121.9 (3)
C4—C1—H1A	109.3	C8—C7—Br1	119.2 (3)
C2—C1—H1A	109.3	C6—C7—Br1	118.8 (3)
C4—C1—H1B	109.3	C7—C8—C9	118.2 (3)
C2—C1—H1B	109.3	C7—C8—H8	120.9
H1A—C1—H1B	108.0	C9—C8—H8	120.9
C1—C2—C3	113.4 (3)	C4—C9—C8	121.7 (3)
C1—C2—H2A	108.9	C4—C9—H9	119.1
C3—C2—H2A	108.9	C8—C9—H9	119.1
C1—C2—H2B	108.9	C15—C10—C11	118.1 (3)
C3—C2—H2B	108.9	C15—C10—C3	121.0 (3)
H2A—C2—H2B	107.7	C11—C10—C3	120.8 (3)
C10—C3—C2	112.4 (3)	C12—C11—C10	121.3 (3)
C10—C3—H3A	109.1	C12—C11—H11	119.4
C2—C3—H3A	109.1	C10—C11—H11	119.4
C10—C3—H3B	109.1	C13—C12—C11	118.8 (3)
C2—C3—H3B	109.1	C13—C12—H12	120.6
H3A—C3—H3B	107.9	C11—C12—H12	120.6
C9—C4—C5	118.3 (3)	C14—C13—C12	121.0 (3)
C9—C4—C1	120.9 (3)	C14—C13—Br2	119.6 (3)
C5—C4—C1	120.8 (3)	C12—C13—Br2	119.4 (2)
C4—C5—C6	121.1 (3)	C13—C14—C15	119.1 (3)
C4—C5—H5	119.4	C13—C14—H14	120.4
C6—C5—H5	119.4	C15—C14—H14	120.4
C7—C6—C5	118.8 (3)	C14—C15—C10	121.6 (3)
C7—C6—H6	120.6	C14—C15—H15	119.2
C5—C6—H6	120.6	C10—C15—H15	119.2

Funding information

Funding for this research was provided by: Defense Threat Reduction Agency (DTRA) - Joint Science and Technology Transfer Office for Chemical and Biological Defense (award No. HDTRA13964); Air Force Office of Scientific Research .

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