Bis[2-(3-bromo­prop­oxy)-5-methyl­phen­yl]methane

Hussain, Z.; Shah, M.R.; Anis, I.; Ng, S.W.

doi:10.1107/S1600536809010587

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o907

doi:10.1107/S1600536809010587

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Bis[2-(3-bromopropoxy)-5-methylphenyl]methane

Zahid Hussain,^a Muhammad Raza Shah,^a Itrat Anis ^a and Seik Weng Ng ^b ^*

^aHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 19 March 2009; accepted 23 March 2009; online 28 March 2009)

The title molecule, C₂₁H₂₆Br₂O₂, is a substituted diphenylmethane derivative whose angle at the methylene carbon is 115.0 (2)°.

Related literature

For the structure of bis[2-(3-bromopropoxy)-5-tert-butylphenyl]methane, see: Yordanov et al. (1995a ,b ).

Experimental

Crystal data

C₂₁H₂₆Br₂O₂
M_r = 470.24
Monoclinic, P 2₁ /c
a = 12.0054 (2) Å
b = 11.9336 (2) Å
c = 14.2827 (2) Å
β = 100.777 (1)°
V = 2010.16 (6) Å³
Z = 4
Mo Kα radiation
μ = 4.04 mm⁻¹
T = 423 K
0.32 × 0.26 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.358, T_max = 0.738
18780 measured reflections
4618 independent reflections
3627 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.079
S = 1.01
4618 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010587/tk2401sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010587/tk2401Isup2.hkl

checkCIF report

Related literature top

For the structure of bis[2-(3-bromopropoxy)-5-tert-butylphenyl]methane, see: Yordanov et al. (1995a,b). [The scheme shows 2-bromoethoxy; please revise]

Experimental top

Potassium carbonate (414 mg, 3 mmol) and 2,2'-methylenebis(4-methylphenol) (228 mg, 1 mmol) in acetone (15 ml) were treated with 1,3-dibromopropane (1.05 g, 5 mmol) at 323 K for 3 h. The solvent was removed under reduced pressure and the residue was dissolved in a mixture of water (50 ml) and dichloromethane (50 ml). The two phases were separated and the aqueous layer extracted with dichloromethane. The dichloromethane solution was dried and the solvent allowed to evaporate slowly to give colorless crystals (182 mg, 80% yield).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) plot of C₂₁H₂₆O₂Br₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Bis[2-(3-bromopropoxy)-5-methylphenyl]methane top

Crystal data top

C₂₁H₂₆Br₂O₂	F(000) = 952
M_r = 470.24	D_x = 1.554 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5910 reflections
a = 12.0054 (2) Å	θ = 2.4–28.1°
b = 11.9336 (2) Å	µ = 4.04 mm⁻¹
c = 14.2827 (2) Å	T = 423 K
β = 100.777 (1)°	Plate, colorless
V = 2010.16 (6) Å³	0.32 × 0.26 × 0.08 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	4618 independent reflections
Radiation source: fine-focus sealed tube	3627 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.358, T_max = 0.738	k = −15→15
18780 measured reflections	l = −18→18

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.034P)² + 1.182P] where P = (F_o² + 2F_c²)/3
4618 reflections	(Δ/σ)_max = 0.001
228 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

C₂₁H₂₆Br₂O₂	V = 2010.16 (6) Å³
M_r = 470.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0054 (2) Å	µ = 4.04 mm⁻¹
b = 11.9336 (2) Å	T = 423 K
c = 14.2827 (2) Å	0.32 × 0.26 × 0.08 mm
β = 100.777 (1)°

Data collection top

Bruker SMART APEX diffractometer	4618 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3627 reflections with I > 2σ(I)
T_min = 0.358, T_max = 0.738	R_int = 0.046
18780 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.01	Δρ_max = 0.48 e Å⁻³
4618 reflections	Δρ_min = −0.62 e Å⁻³
228 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.89529 (2)	0.57379 (2)	0.328900 (19)	0.03798 (9)
Br2	−0.01238 (2)	0.17450 (2)	0.39338 (2)	0.04079 (9)
O1	0.61771 (14)	0.43666 (12)	0.39928 (11)	0.0255 (3)
O2	0.38760 (13)	0.14783 (13)	0.48653 (10)	0.0244 (3)
C1	0.8608 (2)	0.4599 (2)	0.41785 (17)	0.0291 (5)
H1A	0.8199	0.3970	0.3814	0.035*
H1B	0.9325	0.4303	0.4552	0.035*
C2	0.7896 (2)	0.5065 (2)	0.48479 (16)	0.0290 (5)
H2A	0.7851	0.4499	0.5347	0.035*
H2B	0.8280	0.5734	0.5167	0.035*
C3	0.6711 (2)	0.53852 (19)	0.43790 (17)	0.0277 (5)
H3A	0.6297	0.5714	0.4851	0.033*
H3B	0.6728	0.5940	0.3866	0.033*
C4	0.5034 (2)	0.43657 (19)	0.36428 (15)	0.0229 (5)
C5	0.4379 (2)	0.5323 (2)	0.34459 (16)	0.0283 (5)
H5	0.4712	0.6042	0.3575	0.034*
C6	0.3231 (2)	0.5226 (2)	0.30578 (17)	0.0306 (5)
H6	0.2789	0.5886	0.2918	0.037*
C7	0.2715 (2)	0.4188 (2)	0.28700 (15)	0.0270 (5)
C8	0.3394 (2)	0.32366 (19)	0.30820 (15)	0.0226 (5)
H8	0.3055	0.2519	0.2960	0.027*
C9	0.45441 (19)	0.32978 (18)	0.34640 (14)	0.0206 (4)
C10	0.1470 (2)	0.4079 (2)	0.24627 (18)	0.0360 (6)
H10A	0.1241	0.4675	0.1994	0.054*
H10B	0.1035	0.4143	0.2977	0.054*
H10C	0.1323	0.3348	0.2152	0.054*
C11	0.52599 (19)	0.22530 (18)	0.36524 (14)	0.0208 (4)
H11A	0.5910	0.2323	0.3320	0.025*
H11B	0.4801	0.1605	0.3372	0.025*
C12	0.57131 (19)	0.20078 (17)	0.46953 (14)	0.0198 (4)
C13	0.6855 (2)	0.21308 (18)	0.50828 (15)	0.0231 (5)
H13	0.7348	0.2410	0.4688	0.028*
C14	0.7311 (2)	0.18620 (19)	0.60292 (16)	0.0257 (5)
C15	0.6577 (2)	0.1448 (2)	0.65809 (16)	0.0281 (5)
H15	0.6867	0.1251	0.7225	0.034*
C16	0.5428 (2)	0.1311 (2)	0.62258 (16)	0.0269 (5)
H16	0.4941	0.1028	0.6623	0.032*
C17	0.49961 (19)	0.15936 (17)	0.52813 (15)	0.0213 (5)
C18	0.8558 (2)	0.2004 (2)	0.64178 (18)	0.0346 (6)
H18A	0.8995	0.1754	0.5941	0.052*
H18B	0.8771	0.1556	0.6998	0.052*
H18C	0.8722	0.2796	0.6567	0.052*
C19	0.3171 (2)	0.0874 (2)	0.53991 (17)	0.0278 (5)
H19A	0.3126	0.1280	0.5996	0.033*
H19B	0.3492	0.0121	0.5568	0.033*
C20	0.2007 (2)	0.07720 (19)	0.47873 (18)	0.0290 (5)
H20A	0.2074	0.0462	0.4157	0.035*
H20B	0.1545	0.0246	0.5091	0.035*
C21	0.1424 (2)	0.1886 (2)	0.46541 (18)	0.0298 (5)
H21A	0.1860	0.2396	0.4311	0.036*
H21B	0.1404	0.2219	0.5286	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03685 (16)	0.04009 (16)	0.04195 (15)	−0.00652 (11)	0.02015 (12)	−0.00002 (11)
Br2	0.03188 (16)	0.04527 (17)	0.04445 (16)	0.00566 (12)	0.00512 (12)	−0.00249 (12)
O1	0.0253 (9)	0.0198 (8)	0.0330 (8)	−0.0047 (6)	0.0098 (7)	−0.0048 (6)
O2	0.0219 (8)	0.0286 (9)	0.0237 (8)	−0.0027 (7)	0.0068 (7)	0.0033 (6)
C1	0.0291 (13)	0.0257 (12)	0.0311 (12)	−0.0052 (10)	0.0018 (10)	−0.0029 (10)
C2	0.0379 (14)	0.0246 (13)	0.0247 (11)	−0.0104 (10)	0.0060 (10)	−0.0057 (9)
C3	0.0350 (14)	0.0217 (12)	0.0297 (12)	−0.0072 (10)	0.0149 (10)	−0.0062 (9)
C4	0.0262 (12)	0.0245 (12)	0.0207 (10)	0.0005 (9)	0.0111 (9)	0.0017 (9)
C5	0.0365 (14)	0.0224 (12)	0.0296 (12)	0.0019 (10)	0.0152 (10)	0.0022 (9)
C6	0.0384 (15)	0.0274 (13)	0.0290 (12)	0.0102 (11)	0.0141 (11)	0.0075 (10)
C7	0.0273 (13)	0.0347 (13)	0.0203 (10)	0.0050 (10)	0.0080 (9)	0.0023 (9)
C8	0.0250 (12)	0.0248 (11)	0.0191 (10)	−0.0009 (9)	0.0067 (9)	0.0006 (9)
C9	0.0251 (12)	0.0225 (11)	0.0156 (9)	0.0013 (9)	0.0079 (8)	0.0013 (8)
C10	0.0287 (14)	0.0459 (16)	0.0325 (13)	0.0088 (11)	0.0033 (11)	0.0040 (11)
C11	0.0239 (12)	0.0205 (11)	0.0191 (10)	−0.0006 (9)	0.0065 (9)	−0.0022 (8)
C12	0.0242 (12)	0.0151 (10)	0.0203 (10)	0.0019 (8)	0.0050 (9)	−0.0028 (8)
C13	0.0258 (12)	0.0177 (11)	0.0264 (11)	−0.0024 (9)	0.0061 (9)	−0.0017 (9)
C14	0.0265 (13)	0.0204 (11)	0.0278 (11)	0.0004 (9)	−0.0009 (9)	−0.0054 (9)
C15	0.0332 (14)	0.0296 (13)	0.0189 (10)	0.0048 (10)	−0.0015 (10)	0.0001 (9)
C16	0.0320 (14)	0.0266 (12)	0.0238 (11)	0.0012 (10)	0.0097 (10)	0.0019 (9)
C17	0.0227 (12)	0.0183 (11)	0.0227 (10)	0.0008 (9)	0.0042 (9)	−0.0014 (8)
C18	0.0270 (14)	0.0361 (15)	0.0370 (13)	−0.0005 (11)	−0.0037 (11)	−0.0039 (11)
C19	0.0281 (13)	0.0241 (12)	0.0338 (12)	−0.0028 (10)	0.0125 (10)	0.0036 (10)
C20	0.0259 (13)	0.0224 (12)	0.0412 (13)	−0.0036 (10)	0.0124 (10)	−0.0024 (10)
C21	0.0314 (14)	0.0244 (12)	0.0351 (12)	−0.0001 (10)	0.0096 (11)	−0.0038 (10)

Geometric parameters (Å, º) top

Br1—C1	1.957 (2)	C10—H10B	0.9800
Br2—C21	1.956 (3)	C10—H10C	0.9800
O1—C4	1.369 (3)	C11—C12	1.516 (3)
O1—C3	1.436 (3)	C11—H11A	0.9900
O2—C17	1.372 (3)	C11—H11B	0.9900
O2—C19	1.435 (3)	C12—C13	1.387 (3)
C1—C2	1.503 (3)	C12—C17	1.398 (3)
C1—H1A	0.9900	C13—C14	1.398 (3)
C1—H1B	0.9900	C13—H13	0.9500
C2—C3	1.503 (4)	C14—C15	1.379 (3)
C2—H2A	0.9900	C14—C18	1.506 (3)
C2—H2B	0.9900	C15—C16	1.388 (3)
C3—H3A	0.9900	C15—H15	0.9500
C3—H3B	0.9900	C16—C17	1.393 (3)
C4—C5	1.386 (3)	C16—H16	0.9500
C4—C9	1.407 (3)	C18—H18A	0.9800
C5—C6	1.391 (4)	C18—H18B	0.9800
C5—H5	0.9500	C18—H18C	0.9800
C6—C7	1.389 (4)	C19—C20	1.509 (3)
C6—H6	0.9500	C19—H19A	0.9900
C7—C8	1.397 (3)	C19—H19B	0.9900
C7—C10	1.505 (3)	C20—C21	1.497 (3)
C8—C9	1.388 (3)	C20—H20A	0.9900
C8—H8	0.9500	C20—H20B	0.9900
C9—C11	1.510 (3)	C21—H21A	0.9900
C10—H10A	0.9800	C21—H21B	0.9900

C4—O1—C3	119.08 (18)	C12—C11—H11A	108.5
C17—O2—C19	116.61 (17)	C9—C11—H11B	108.5
C2—C1—Br1	111.78 (17)	C12—C11—H11B	108.5
C2—C1—H1A	109.3	H11A—C11—H11B	107.5
Br1—C1—H1A	109.3	C13—C12—C17	118.14 (19)
C2—C1—H1B	109.3	C13—C12—C11	121.2 (2)
Br1—C1—H1B	109.3	C17—C12—C11	120.6 (2)
H1A—C1—H1B	107.9	C12—C13—C14	122.8 (2)
C3—C2—C1	114.44 (19)	C12—C13—H13	118.6
C3—C2—H2A	108.6	C14—C13—H13	118.6
C1—C2—H2A	108.6	C15—C14—C13	117.3 (2)
C3—C2—H2B	108.6	C15—C14—C18	121.8 (2)
C1—C2—H2B	108.6	C13—C14—C18	120.9 (2)
H2A—C2—H2B	107.6	C14—C15—C16	122.1 (2)
O1—C3—C2	105.84 (19)	C14—C15—H15	118.9
O1—C3—H3A	110.6	C16—C15—H15	118.9
C2—C3—H3A	110.6	C15—C16—C17	119.3 (2)
O1—C3—H3B	110.6	C15—C16—H16	120.3
C2—C3—H3B	110.6	C17—C16—H16	120.3
H3A—C3—H3B	108.7	O2—C17—C16	123.5 (2)
O1—C4—C5	124.4 (2)	O2—C17—C12	116.07 (18)
O1—C4—C9	115.06 (19)	C16—C17—C12	120.4 (2)
C5—C4—C9	120.5 (2)	C14—C18—H18A	109.5
C4—C5—C6	119.7 (2)	C14—C18—H18B	109.5
C4—C5—H5	120.2	H18A—C18—H18B	109.5
C6—C5—H5	120.2	C14—C18—H18C	109.5
C7—C6—C5	121.6 (2)	H18A—C18—H18C	109.5
C7—C6—H6	119.2	H18B—C18—H18C	109.5
C5—C6—H6	119.2	O2—C19—C20	107.90 (19)
C6—C7—C8	117.5 (2)	O2—C19—H19A	110.1
C6—C7—C10	121.8 (2)	C20—C19—H19A	110.1
C8—C7—C10	120.7 (2)	O2—C19—H19B	110.1
C9—C8—C7	122.7 (2)	C20—C19—H19B	110.1
C9—C8—H8	118.7	H19A—C19—H19B	108.4
C7—C8—H8	118.7	C21—C20—C19	111.2 (2)
C8—C9—C4	118.1 (2)	C21—C20—H20A	109.4
C8—C9—C11	121.2 (2)	C19—C20—H20A	109.4
C4—C9—C11	120.7 (2)	C21—C20—H20B	109.4
C7—C10—H10A	109.5	C19—C20—H20B	109.4
C7—C10—H10B	109.5	H20A—C20—H20B	108.0
H10A—C10—H10B	109.5	C20—C21—Br2	111.45 (17)
C7—C10—H10C	109.5	C20—C21—H21A	109.3
H10A—C10—H10C	109.5	Br2—C21—H21A	109.3
H10B—C10—H10C	109.5	C20—C21—H21B	109.3
C9—C11—C12	114.98 (17)	Br2—C21—H21B	109.3
C9—C11—H11A	108.5	H21A—C21—H21B	108.0

Br1—C1—C2—C3	67.6 (2)	C9—C11—C12—C13	−109.0 (2)
C4—O1—C3—C2	170.44 (18)	C9—C11—C12—C17	74.4 (3)
C1—C2—C3—O1	62.5 (2)	C17—C12—C13—C14	−0.2 (3)
C3—O1—C4—C5	14.2 (3)	C11—C12—C13—C14	−176.9 (2)
C3—O1—C4—C9	−167.37 (18)	C12—C13—C14—C15	0.7 (3)
O1—C4—C5—C6	177.6 (2)	C12—C13—C14—C18	179.7 (2)
C9—C4—C5—C6	−0.8 (3)	C13—C14—C15—C16	−0.7 (3)
C4—C5—C6—C7	0.7 (3)	C18—C14—C15—C16	−179.8 (2)
C5—C6—C7—C8	−0.3 (3)	C14—C15—C16—C17	0.3 (4)
C5—C6—C7—C10	179.2 (2)	C19—O2—C17—C16	−10.0 (3)
C6—C7—C8—C9	−0.2 (3)	C19—O2—C17—C12	169.29 (19)
C10—C7—C8—C9	−179.6 (2)	C15—C16—C17—O2	179.4 (2)
C7—C8—C9—C4	0.1 (3)	C15—C16—C17—C12	0.2 (3)
C7—C8—C9—C11	−177.87 (19)	C13—C12—C17—O2	−179.52 (18)
O1—C4—C9—C8	−178.16 (18)	C11—C12—C17—O2	−2.8 (3)
C5—C4—C9—C8	0.4 (3)	C13—C12—C17—C16	−0.2 (3)
O1—C4—C9—C11	−0.2 (3)	C11—C12—C17—C16	176.5 (2)
C5—C4—C9—C11	178.35 (19)	C17—O2—C19—C20	−175.85 (18)
C8—C9—C11—C12	−113.2 (2)	O2—C19—C20—C21	−69.0 (3)
C4—C9—C11—C12	68.9 (3)	C19—C20—C21—Br2	−176.17 (16)

Experimental details

Crystal data
Chemical formula	C₂₁H₂₆Br₂O₂
M_r	470.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	423
a, b, c (Å)	12.0054 (2), 11.9336 (2), 14.2827 (2)
β (°)	100.777 (1)
V (Å³)	2010.16 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.04
Crystal size (mm)	0.32 × 0.26 × 0.08

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.358, 0.738
No. of measured, independent and observed [I > 2σ(I)] reflections	18780, 4618, 3627
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 1.01
No. of reflections	4618
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.62

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

We thank the Higher Education Commission of Pakistan and the University of Malaya for supporting this study.

References

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