Bis[5-chloro-2-(prop-2-yn-1-yl­oxy)phen­yl]methane

Ali, Q.; Anis, I.; Raza Shah, M.; Ng, S.W.

doi:10.1107/S1600536811003205

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o530

doi:10.1107/S1600536811003205

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Bis[5-chloro-2-(prop-2-yn-1-yloxy)phenyl]methane

Qamar Ali,^a Itrat Anis,^a M. Raza Shah ^a and Seik Weng Ng ^b ^*

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 7527, Pakistan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 22 January 2011; accepted 25 January 2011; online 29 January 2011)

The molecule of the title compound, C₁₉H₁₄Cl₂O₂, has two benzene rings connected to a methylene C atom, and the rings are aligned at 66.3 (1)°. Intermolecular C—H⋯π and π–π stacking interactions are observed in the crystal structure, the centroid–centroid distances between parallel benzene rings being 3.7529 (12) and 3.6201 (12) Å, respectively.

Related literature

For a related structure, see: Hussain et al. (2009 ).

Experimental

Crystal data

C₁₉H₁₄Cl₂O₂
M_r = 345.20
Triclinic, $[P \overline 1]$
a = 8.4844 (5) Å
b = 9.7845 (6) Å
c = 11.2568 (6) Å
α = 86.258 (5)°
β = 71.412 (5)°
γ = 64.707 (6)°
V = 798.08 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.815, T_max = 1.000
6118 measured reflections
3523 independent reflections
2975 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.099
S = 1.00
3523 reflections
216 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C11–C16 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Cgⁱ	0.95	2.60	3.471 (2)	153
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003205/xu5147sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003205/xu5147Isup2.hkl

checkCIF report

Comment top

We have reported several compounds that adopt a V-shape; this shape is induced by a methylene linkage to two aromatic systems. An example is bis[2-(3-bromopropoxy)-5-methylphenyl]methane, which methyl carbon has a widened angle of 115.0 (2)° (Hussain et al., 2009). The methylene angle in the present compound (Scheme I, Fig. 1) is similar [114.4 (1) °]. Two two aromatic rings that are connected the methylene carbon are aligned at 66.3 (1)°. Intermolecular C—H···π interaction occurs between inversion center related molecules (Table 1). π-π stacking is also present between parallel benzene rings in the crystal structure, centroid-to-centroid distances being 3.7529 (12) Å between C1-ring and C1ⁱ-ring (symmetry code: (i) 1-x, 1-y, 1-z), and 3.6201 (12) Å between C11-ring and C11ⁱⁱ-ring (symmetry code: (ii) 2-x, 1-y, -z).

Related literature top

For a related structure, see: Hussain et al. (2009).

Experimental top

2, 2'-Methylenebis(4-chlorophenol) (1 g, 3.7 mmol) was dissolved in ethanol (30 ml). Potassium carbonate (1.5 g, 11 mmol) was added and the mixture was heated for an hour. Propargyl bromide (2 ml, 22 mmol) was added and the heating continues for another 3 h. Water (50 ml) was added. The organic compound was extracted by ethyl acetate (50 ml). Slow evaporation of ethyl acetate solution afforded crystals in 80% yield.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₉H₁₄Cl₂O₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Bis[5-chloro-2-(prop-2-yn-1-yloxy)phenyl]methane top

Crystal data top

C₁₉H₁₄Cl₂O₂	Z = 2
M_r = 345.20	F(000) = 356
Triclinic, P1	D_x = 1.436 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4844 (5) Å	Cell parameters from 3298 reflections
b = 9.7845 (6) Å	θ = 2.3–29.2°
c = 11.2568 (6) Å	µ = 0.41 mm⁻¹
α = 86.258 (5)°	T = 100 K
β = 71.412 (5)°	Prism, colorless
γ = 64.707 (6)°	0.30 × 0.25 × 0.20 mm
V = 798.08 (8) Å³

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	3523 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2975 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −9→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −10→12
T_min = 0.815, T_max = 1.000	l = −11→14
6118 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0454P)² + 0.2682P] where P = (F_o² + 2F_c²)/3
3523 reflections	(Δ/σ)_max = 0.001
216 parameters	Δρ_max = 0.30 e Å⁻³
2 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₉H₁₄Cl₂O₂	γ = 64.707 (6)°
M_r = 345.20	V = 798.08 (8) Å³
Triclinic, P1	Z = 2
a = 8.4844 (5) Å	Mo Kα radiation
b = 9.7845 (6) Å	µ = 0.41 mm⁻¹
c = 11.2568 (6) Å	T = 100 K
α = 86.258 (5)°	0.30 × 0.25 × 0.20 mm
β = 71.412 (5)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	3523 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2975 reflections with I > 2σ(I)
T_min = 0.815, T_max = 1.000	R_int = 0.029
6118 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	2 restraints
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.30 e Å⁻³
3523 reflections	Δρ_min = −0.35 e Å⁻³
216 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.85099 (6)	0.23350 (5)	0.67998 (4)	0.02285 (13)
Cl2	0.50877 (6)	0.78470 (5)	−0.01311 (4)	0.02450 (13)
O1	0.55177 (16)	0.77464 (14)	0.41682 (11)	0.0196 (3)
O2	1.00711 (16)	0.26968 (13)	0.18471 (11)	0.0182 (3)
C1	0.3290 (3)	1.1163 (2)	0.32429 (18)	0.0228 (4)
C2	0.3478 (2)	1.0165 (2)	0.39167 (16)	0.0182 (4)
C3	0.3745 (2)	0.89566 (19)	0.47714 (16)	0.0175 (4)
H3A	0.3701	0.9327	0.5584	0.021*
H3B	0.2769	0.8603	0.4932	0.021*
C4	0.6114 (2)	0.65014 (19)	0.48288 (15)	0.0158 (4)
C5	0.5100 (2)	0.6355 (2)	0.60376 (16)	0.0176 (4)
H5	0.3909	0.7132	0.6444	0.021*
C6	0.5838 (2)	0.5070 (2)	0.66444 (16)	0.0176 (4)
H6	0.5161	0.4960	0.7469	0.021*
C7	0.7568 (2)	0.3954 (2)	0.60351 (16)	0.0176 (4)
C8	0.8582 (2)	0.4087 (2)	0.48282 (16)	0.0172 (4)
H8	0.9766	0.3300	0.4425	0.021*
C9	0.7868 (2)	0.5366 (2)	0.42099 (15)	0.0154 (3)
C10	0.8966 (2)	0.5563 (2)	0.29023 (15)	0.0161 (4)
H10A	0.8890	0.6602	0.2891	0.019*
H10B	1.0276	0.4843	0.2730	0.019*
C11	0.8327 (2)	0.5312 (2)	0.18567 (15)	0.0151 (3)
C12	0.7154 (2)	0.6527 (2)	0.13844 (16)	0.0170 (4)
H12	0.6728	0.7530	0.1729	0.020*
C13	0.6599 (2)	0.6288 (2)	0.04161 (16)	0.0172 (4)
C14	0.7199 (2)	0.4852 (2)	−0.01130 (16)	0.0178 (4)
H14	0.6819	0.4705	−0.0783	0.021*
C15	0.8372 (2)	0.3614 (2)	0.03478 (16)	0.0167 (4)
H15	0.8794	0.2615	−0.0005	0.020*
C16	0.8922 (2)	0.38484 (19)	0.13286 (15)	0.0155 (3)
C17	1.0784 (2)	0.1178 (2)	0.13135 (17)	0.0199 (4)
H17A	1.1792	0.0504	0.1634	0.024*
H17B	1.1309	0.1149	0.0389	0.024*
C18	0.9368 (2)	0.0606 (2)	0.16123 (16)	0.0196 (4)
C19	0.8221 (3)	0.0152 (2)	0.18736 (17)	0.0232 (4)
H1	0.317 (3)	1.1950 (19)	0.2701 (17)	0.033 (6)*
H19	0.729 (2)	−0.020 (3)	0.209 (2)	0.039 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0291 (3)	0.0206 (2)	0.0249 (2)	−0.0126 (2)	−0.01521 (19)	0.00937 (18)
Cl2	0.0240 (2)	0.0226 (3)	0.0224 (2)	−0.0051 (2)	−0.00986 (18)	0.00816 (18)
O1	0.0207 (6)	0.0165 (6)	0.0147 (6)	−0.0038 (5)	−0.0032 (5)	0.0024 (5)
O2	0.0191 (6)	0.0138 (6)	0.0207 (6)	−0.0033 (5)	−0.0100 (5)	−0.0003 (5)
C1	0.0210 (9)	0.0223 (10)	0.0237 (10)	−0.0072 (8)	−0.0089 (7)	0.0042 (8)
C2	0.0143 (8)	0.0201 (9)	0.0187 (9)	−0.0053 (7)	−0.0055 (7)	−0.0031 (7)
C3	0.0150 (8)	0.0176 (9)	0.0174 (9)	−0.0046 (7)	−0.0049 (7)	−0.0006 (7)
C4	0.0191 (9)	0.0154 (8)	0.0145 (8)	−0.0074 (7)	−0.0074 (7)	0.0012 (7)
C5	0.0173 (8)	0.0191 (9)	0.0161 (9)	−0.0080 (7)	−0.0046 (7)	−0.0002 (7)
C6	0.0200 (9)	0.0209 (9)	0.0151 (8)	−0.0120 (8)	−0.0056 (7)	0.0026 (7)
C7	0.0229 (9)	0.0185 (9)	0.0182 (9)	−0.0120 (8)	−0.0115 (7)	0.0052 (7)
C8	0.0166 (8)	0.0175 (9)	0.0194 (9)	−0.0075 (7)	−0.0077 (7)	0.0002 (7)
C9	0.0171 (8)	0.0182 (9)	0.0146 (8)	−0.0103 (7)	−0.0057 (6)	0.0004 (7)
C10	0.0156 (8)	0.0169 (9)	0.0161 (8)	−0.0074 (7)	−0.0049 (6)	0.0011 (7)
C11	0.0137 (8)	0.0191 (9)	0.0138 (8)	−0.0097 (7)	−0.0023 (6)	0.0019 (7)
C12	0.0177 (8)	0.0164 (9)	0.0153 (8)	−0.0091 (7)	−0.0011 (6)	0.0021 (7)
C13	0.0143 (8)	0.0197 (9)	0.0140 (8)	−0.0059 (7)	−0.0029 (6)	0.0061 (7)
C14	0.0155 (8)	0.0246 (10)	0.0141 (8)	−0.0093 (8)	−0.0050 (6)	0.0022 (7)
C15	0.0172 (8)	0.0177 (9)	0.0138 (8)	−0.0072 (7)	−0.0037 (6)	−0.0003 (7)
C16	0.0132 (8)	0.0180 (9)	0.0141 (8)	−0.0065 (7)	−0.0035 (6)	0.0035 (7)
C17	0.0188 (9)	0.0151 (9)	0.0213 (9)	−0.0023 (7)	−0.0068 (7)	−0.0026 (7)
C18	0.0232 (9)	0.0155 (9)	0.0151 (9)	−0.0029 (8)	−0.0070 (7)	−0.0012 (7)
C19	0.0279 (10)	0.0231 (10)	0.0172 (9)	−0.0107 (9)	−0.0056 (7)	−0.0002 (7)

Geometric parameters (Å, º) top

Cl1—C7	1.7518 (18)	C8—H8	0.9500
Cl2—C13	1.7492 (18)	C9—C10	1.521 (2)
O1—C4	1.374 (2)	C10—C11	1.516 (2)
O1—C3	1.435 (2)	C10—H10A	0.9900
O2—C16	1.378 (2)	C10—H10B	0.9900
O2—C17	1.432 (2)	C11—C12	1.389 (2)
C1—C2	1.183 (3)	C11—C16	1.400 (2)
C1—H1	0.94 (2)	C12—C13	1.385 (2)
C2—C3	1.462 (2)	C12—H12	0.9500
C3—H3A	0.9900	C13—C14	1.376 (3)
C3—H3B	0.9900	C14—C15	1.394 (2)
C4—C9	1.401 (2)	C14—H14	0.9500
C4—C5	1.395 (2)	C15—C16	1.394 (2)
C5—C6	1.389 (2)	C15—H15	0.9500
C5—H5	0.9500	C17—C18	1.470 (3)
C6—C7	1.379 (3)	C17—H17A	0.9900
C6—H6	0.9500	C17—H17B	0.9900
C7—C8	1.389 (2)	C18—C19	1.184 (3)
C8—C9	1.387 (2)	C19—H19	0.95 (2)

C4—O1—C3	117.28 (13)	C9—C10—H10A	108.7
C16—O2—C17	117.67 (13)	C11—C10—H10B	108.7
C2—C1—H1	178.8 (13)	C9—C10—H10B	108.7
C1—C2—C3	177.80 (19)	H10A—C10—H10B	107.6
O1—C3—C2	106.72 (13)	C12—C11—C16	118.08 (15)
O1—C3—H3A	110.4	C12—C11—C10	121.02 (15)
C2—C3—H3A	110.4	C16—C11—C10	120.89 (15)
O1—C3—H3B	110.4	C13—C12—C11	120.63 (16)
C2—C3—H3B	110.4	C13—C12—H12	119.7
H3A—C3—H3B	108.6	C11—C12—H12	119.7
O1—C4—C9	115.07 (14)	C14—C13—C12	121.33 (16)
O1—C4—C5	123.85 (15)	C14—C13—Cl2	119.55 (14)
C9—C4—C5	121.06 (16)	C12—C13—Cl2	119.12 (14)
C6—C5—C4	119.73 (16)	C13—C14—C15	119.11 (16)
C6—C5—H5	120.1	C13—C14—H14	120.4
C4—C5—H5	120.1	C15—C14—H14	120.4
C7—C6—C5	119.16 (16)	C14—C15—C16	119.73 (16)
C7—C6—H6	120.4	C14—C15—H15	120.1
C5—C6—H6	120.4	C16—C15—H15	120.1
C6—C7—C8	121.46 (16)	O2—C16—C15	123.84 (16)
C6—C7—Cl1	119.33 (13)	O2—C16—C11	115.05 (15)
C8—C7—Cl1	119.21 (14)	C15—C16—C11	121.11 (16)
C9—C8—C7	120.16 (16)	O2—C17—C18	112.48 (14)
C9—C8—H8	119.9	O2—C17—H17A	109.1
C7—C8—H8	119.9	C18—C17—H17A	109.1
C8—C9—C4	118.44 (15)	O2—C17—H17B	109.1
C8—C9—C10	121.38 (15)	C18—C17—H17B	109.1
C4—C9—C10	120.17 (15)	H17A—C17—H17B	107.8
C11—C10—C9	114.36 (13)	C19—C18—C17	178.90 (19)
C11—C10—H10A	108.7	C18—C19—H19	179.4 (15)

C4—O1—C3—C2	176.88 (13)	C9—C10—C11—C12	97.47 (18)
C3—O1—C4—C9	−178.72 (14)	C9—C10—C11—C16	−83.30 (19)
C3—O1—C4—C5	0.0 (2)	C16—C11—C12—C13	−0.2 (2)
O1—C4—C5—C6	−178.32 (15)	C10—C11—C12—C13	179.03 (15)
C9—C4—C5—C6	0.3 (3)	C11—C12—C13—C14	−0.5 (2)
C4—C5—C6—C7	−0.2 (3)	C11—C12—C13—Cl2	178.86 (12)
C5—C6—C7—C8	−0.2 (3)	C12—C13—C14—C15	0.8 (2)
C5—C6—C7—Cl1	179.66 (13)	Cl2—C13—C14—C15	−178.63 (13)
C6—C7—C8—C9	0.5 (3)	C13—C14—C15—C16	−0.2 (2)
Cl1—C7—C8—C9	−179.40 (12)	C17—O2—C16—C15	2.2 (2)
C7—C8—C9—C4	−0.3 (2)	C17—O2—C16—C11	−177.57 (14)
C7—C8—C9—C10	178.34 (15)	C14—C15—C16—O2	179.79 (15)
O1—C4—C9—C8	178.68 (14)	C14—C15—C16—C11	−0.5 (2)
C5—C4—C9—C8	−0.1 (2)	C12—C11—C16—O2	−179.54 (14)
O1—C4—C9—C10	0.0 (2)	C10—C11—C16—O2	1.2 (2)
C5—C4—C9—C10	−178.76 (15)	C12—C11—C16—C15	0.7 (2)
C8—C9—C10—C11	105.02 (18)	C10—C11—C16—C15	−178.53 (15)
C4—C9—C10—C11	−76.4 (2)	C16—O2—C17—C18	−71.59 (19)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C11–C16 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cgⁱ	0.95	2.60	3.471 (2)	153

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₄Cl₂O₂
M_r	345.20
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.4844 (5), 9.7845 (6), 11.2568 (6)
α, β, γ (°)	86.258 (5), 71.412 (5), 64.707 (6)
V (Å³)	798.08 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.815, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6118, 3523, 2975
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.099, 1.00
No. of reflections	3523
No. of parameters	216
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.35

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C11–C16 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cgⁱ	0.95	2.60	3.471 (2)	153

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Hussain, Z., Shah, M. R., Anis, I. & Ng, S. W. (2009). Acta Cryst. E65, o907. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Volume 67| Part 2| February 2011| Page o530

doi:10.1107/S1600536811003205

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