Methyl 2-{4-chloro-2-[5-chloro-2-(2-meth­oxy-2-oxoeth­oxy)benz­yl]phen­oxy}acetate

Abstract

In the crystal structure of the title compound, C₁₉H₁₈Cl₂O₆, mol­ecules are connected via weak C—H⋯π inter­actions into closely packed dimers.

Related literature  

For the synthesis, see: Ertul et al. (2009 ▶).

Experimental  

Crystal data  

• C₁₉H₁₈Cl₂O₆

• M _r = 413.23

• Triclinic,

• a = 7.4727 (6) Å

• b = 10.4704 (8) Å

• c = 12.2796 (8) Å

• α = 90.384 (6)°

• β = 100.716 (6)°

• γ = 94.365 (6)°

• V = 941.08 (12) ų

• Z = 2

• Cu Kα radiation

• μ = 3.41 mm⁻¹

• T = 120 K

• 0.45 × 0.09 × 0.04 mm

Data collection  

• Agilent Xcalibur Atlas Gemini ultra diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.258, T _max = 1.000

• 8465 measured reflections

• 3319 independent reflections

• 2606 reflections with I > 2σ(I)

• R _int = 0.085

Refinement  

• R[F ² > 2σ(F ²)] = 0.080

• wR(F ²) = 0.239

• S = 1.02

• 3319 reflections

• 244 parameters

• H-atom parameters constrained

• Δρ_max = 0.92 e Å⁻³

• Δρ_min = −0.64 e Å⁻³

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: Mercury (Macrae et al., 2006 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681202555X/vm2175Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 aromatic rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Cg1i	0.93	2.72	3.500 (3)	142
C17—H17A⋯Cg2i	0.97	2.67	3.450 (3)	138

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound is an intermediate in the synthesis of cyclic lactams (Ertul et al., 2009). The molecule consists of two phenyl rings substituted with a chlorine atom in para position (Fig. 1). The dihedral angle between the planes of the two aromatic rings is 72.40 (14)°. The arrangement of the molecules is influenced by C—H···π interactions between two neighbouring molecules leading to the formation of closely packed dimers (Table 1, Fig. 2). Due to the presence of aromatic rings, the molecules are also connected via system of π–π interactions (Cg1···Cg2ⁱ: 4.7735 (17) Å; Cg1 and Cg2 are the centroids of rings C1-C6 and C8-C13, respectively; symmetry code: (i) 1 -x, 1 - y, 2 - z).

Experimental

All chemicals used were purchased from Fluka and used without further purification. The title compound was synthesized by means of the method published by Ertul et al. (2009). Crystals were prepared by sublimation (mp. 125 °C, elemental analysis for C₁₉H₁₈Cl₂O: calculated C 55.22, H 4.39; found C 55.20, H 4.41).

Refinement

The H atoms were all located in a difference map and repositioned geometrically. The distance between C and H atoms depends on the carbon atom type and are in a range of 0.93–0.97 Å. The isotropic temperature parameters of hydrogen atoms were calculated as 1.2U_eq of the parent atom.

Figures

Fig. 1.

View of the title compound, together with atom-labelling scheme. Displacement ellipsoids are shown at the 50% probability level.

Fig. 2.

Projection along the c axis with highlighted C—H···π interactions.

Crystal data

C19H18Cl2O6	Z = 2
Mr = 413.23	F(000) = 428
Triclinic, P1	Dx = 1.458 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.5418 Å
a = 7.4727 (6) Å	Cell parameters from 5088 reflections
b = 10.4704 (8) Å	θ = 3.7–66.8°
c = 12.2796 (8) Å	µ = 3.41 mm−1
α = 90.384 (6)°	T = 120 K
β = 100.716 (6)°	Needle, colourless
γ = 94.365 (6)°	0.45 × 0.09 × 0.04 mm
V = 941.08 (12) Å3

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer	3319 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2606 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.085
Detector resolution: 10.3784 pixels mm-1	θmax = 66.9°, θmin = 3.7°
Rotation method data acquisition using ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→12
Tmin = 0.258, Tmax = 1.000	l = −14→13
8465 measured reflections

Refinement

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.239	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.184P)2] where P = (Fo2 + 2Fc2)/3
3319 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.92 e Å−3
0 restraints	Δρmin = −0.64 e Å−3

Special details

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. The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The distance between C and H atoms depends on the carbon atom type and are in a range of 0.93–0.97 Å. The isotropic temperature parameters of hydrogen atoms were calculated as 1.2*Ueq of the parent atom. Unfortunately, the quality of prepared crystals was very low, which lead to the higher R factors.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C16	0.2502 (6)	1.0126 (5)	1.4550 (4)	0.0432 (11)
H16A	0.1571	1.0210	1.4984	0.065*
H16B	0.3059	1.0958	1.4435	0.065*
H16C	0.3413	0.9607	1.4935	0.065*
Cl1	0.07945 (13)	0.74416 (9)	0.62990 (8)	0.0353 (4)
Cl2	0.79884 (14)	0.69660 (9)	1.38850 (8)	0.0377 (4)
O1	0.3117 (3)	0.8580 (2)	1.1050 (2)	0.0248 (6)
O4	0.6604 (3)	0.6107 (2)	0.9064 (2)	0.0238 (6)
O5	0.6164 (4)	0.5956 (3)	0.6838 (2)	0.0384 (7)
O6	0.7106 (4)	0.3966 (3)	0.6938 (2)	0.0343 (7)
O3	0.4473 (4)	0.9652 (3)	1.3038 (3)	0.0395 (7)
O2	0.1699 (4)	0.9529 (3)	1.3497 (2)	0.0361 (7)
C1	0.2473 (5)	0.8278 (3)	0.9956 (3)	0.0218 (7)
C13	0.6939 (5)	0.6230 (3)	1.0194 (3)	0.0215 (7)
C5	0.3291 (5)	0.7943 (3)	0.8183 (3)	0.0254 (8)
H5	0.4164	0.7883	0.7739	0.030*
C8	0.6565 (4)	0.7415 (3)	1.0613 (3)	0.0227 (8)
C4	0.1439 (5)	0.7769 (3)	0.7713 (3)	0.0258 (8)
C15	0.2866 (5)	0.9364 (3)	1.2822 (3)	0.0281 (8)
C6	0.3832 (5)	0.8203 (3)	0.9305 (3)	0.0224 (8)
C17	0.7040 (5)	0.4958 (3)	0.8609 (3)	0.0247 (8)
H17A	0.6289	0.4241	0.8823	0.030*
H17B	0.8311	0.4818	0.8885	0.030*
C7	0.5825 (5)	0.8440 (3)	0.9824 (3)	0.0223 (8)
H7A	0.6003	0.9256	1.0223	0.027*
H7B	0.6533	0.8509	0.9237	0.027*
C3	0.0112 (5)	0.7825 (3)	0.8353 (3)	0.0255 (8)
H3	−0.1118	0.7694	0.8031	0.031*
C2	0.0634 (5)	0.8080 (3)	0.9482 (3)	0.0234 (8)
H2	−0.0249	0.8118	0.9922	0.028*
C18	0.6699 (5)	0.5054 (3)	0.7362 (3)	0.0275 (8)
C10	0.7594 (5)	0.6685 (4)	1.2466 (3)	0.0279 (8)
C14	0.1824 (5)	0.8784 (3)	1.1734 (3)	0.0256 (8)
H14A	0.1171	0.7979	1.1860	0.031*
H14B	0.0945	0.9360	1.1381	0.031*
C11	0.7946 (5)	0.5516 (3)	1.2058 (3)	0.0275 (8)
H11	0.8394	0.4887	1.2543	0.033*
C12	0.7631 (5)	0.5283 (3)	1.0930 (3)	0.0251 (8)
H12	0.7876	0.4499	1.0654	0.030*
C9	0.6897 (5)	0.7628 (3)	1.1747 (3)	0.0239 (8)
H9	0.6654	0.8408	1.2033	0.029*
C19	0.6900 (7)	0.3897 (5)	0.5742 (4)	0.0423 (10)
H19A	0.7222	0.3076	0.5522	0.063*
H19B	0.7688	0.4560	0.5501	0.063*
H19C	0.5655	0.4008	0.5410	0.063*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C16	0.045 (2)	0.054 (3)	0.033 (2)	0.005 (2)	0.0143 (19)	−0.012 (2)
Cl1	0.0456 (6)	0.0380 (6)	0.0222 (6)	0.0074 (4)	0.0048 (4)	−0.0001 (4)
Cl2	0.0541 (7)	0.0351 (6)	0.0231 (6)	0.0083 (4)	0.0034 (4)	−0.0029 (4)
O1	0.0295 (13)	0.0248 (13)	0.0223 (14)	0.0046 (10)	0.0094 (10)	−0.0002 (10)
O4	0.0349 (13)	0.0184 (12)	0.0202 (13)	0.0044 (10)	0.0096 (10)	0.0001 (10)
O5	0.0581 (18)	0.0313 (15)	0.0285 (16)	0.0131 (13)	0.0108 (13)	0.0047 (12)
O6	0.0534 (17)	0.0296 (14)	0.0231 (15)	0.0105 (12)	0.0127 (12)	−0.0013 (11)
O3	0.0335 (16)	0.0513 (18)	0.0335 (17)	−0.0050 (13)	0.0101 (12)	−0.0115 (14)
O2	0.0357 (14)	0.0468 (16)	0.0280 (16)	0.0029 (12)	0.0123 (11)	−0.0084 (12)
C1	0.0345 (18)	0.0108 (15)	0.0220 (18)	0.0019 (13)	0.0098 (14)	0.0007 (13)
C13	0.0274 (16)	0.0176 (16)	0.0218 (18)	0.0018 (13)	0.0104 (13)	0.0025 (13)
C5	0.0326 (19)	0.0175 (16)	0.028 (2)	0.0039 (14)	0.0109 (15)	0.0040 (14)
C8	0.0233 (16)	0.0169 (16)	0.030 (2)	0.0003 (13)	0.0097 (14)	0.0040 (14)
C4	0.040 (2)	0.0153 (16)	0.0232 (19)	0.0047 (14)	0.0062 (15)	0.0002 (14)
C15	0.038 (2)	0.0222 (18)	0.027 (2)	0.0056 (15)	0.0122 (16)	0.0025 (15)
C6	0.0305 (17)	0.0118 (15)	0.0266 (19)	0.0029 (13)	0.0092 (14)	0.0021 (13)
C17	0.0327 (18)	0.0186 (16)	0.024 (2)	0.0036 (14)	0.0083 (15)	−0.0041 (14)
C7	0.0289 (18)	0.0148 (15)	0.0255 (19)	0.0025 (13)	0.0104 (14)	0.0029 (14)
C3	0.0328 (18)	0.0183 (16)	0.026 (2)	0.0039 (14)	0.0069 (15)	0.0003 (14)
C2	0.0288 (17)	0.0184 (16)	0.0246 (19)	0.0006 (13)	0.0095 (14)	−0.0005 (14)
C18	0.0324 (19)	0.0209 (18)	0.031 (2)	−0.0004 (14)	0.0111 (15)	−0.0014 (15)
C10	0.0318 (18)	0.0253 (18)	0.027 (2)	0.0013 (15)	0.0075 (15)	−0.0006 (15)
C14	0.0319 (18)	0.0243 (18)	0.0230 (19)	0.0023 (14)	0.0116 (14)	−0.0010 (14)
C11	0.0350 (19)	0.0246 (18)	0.024 (2)	0.0042 (15)	0.0068 (15)	0.0039 (15)
C12	0.0323 (18)	0.0172 (16)	0.027 (2)	0.0026 (14)	0.0091 (15)	0.0004 (14)
C9	0.0261 (17)	0.0204 (16)	0.0256 (19)	0.0001 (13)	0.0070 (14)	−0.0020 (14)
C19	0.065 (3)	0.042 (2)	0.023 (2)	0.010 (2)	0.0153 (19)	−0.0062 (18)

Geometric parameters (Å, º)

C16—O2	1.437 (6)	C8—C7	1.517 (5)
C16—H16A	0.9600	C4—C3	1.380 (5)
C16—H16B	0.9600	C15—C14	1.513 (6)
C16—H16C	0.9600	C6—C7	1.508 (5)
Cl1—C4	1.738 (4)	C17—C18	1.510 (5)
Cl2—C10	1.732 (4)	C17—H17A	0.9700
O1—C1	1.367 (4)	C17—H17B	0.9700
O1—C14	1.419 (4)	C7—H7A	0.9700
O4—C13	1.368 (4)	C7—H7B	0.9700
O4—C17	1.409 (4)	C3—C2	1.386 (5)
O5—C18	1.198 (5)	C3—H3	0.9300
O6—C18	1.328 (5)	C2—H2	0.9300
O6—C19	1.449 (5)	C10—C11	1.382 (5)
O3—C15	1.196 (5)	C10—C9	1.394 (5)
O2—C15	1.330 (5)	C14—H14A	0.9700
C1—C2	1.388 (5)	C14—H14B	0.9700
C1—C6	1.411 (5)	C11—C12	1.377 (5)
C13—C8	1.406 (5)	C11—H11	0.9300
C13—C12	1.409 (5)	C12—H12	0.9300
C5—C6	1.381 (5)	C9—H9	0.9300
C5—C4	1.394 (6)	C19—H19A	0.9600
C5—H5	0.9300	C19—H19B	0.9600
C8—C9	1.382 (5)	C19—H19C	0.9600
O2—C16—H16A	109.5	C6—C7—H7A	108.6
O2—C16—H16B	109.5	C8—C7—H7A	108.6
H16A—C16—H16B	109.5	C6—C7—H7B	108.6
O2—C16—H16C	109.5	C8—C7—H7B	108.6
H16A—C16—H16C	109.5	H7A—C7—H7B	107.6
H16B—C16—H16C	109.5	C4—C3—C2	119.2 (3)
C1—O1—C14	117.9 (3)	C4—C3—H3	120.4
C13—O4—C17	117.0 (3)	C2—C3—H3	120.4
C18—O6—C19	116.1 (3)	C3—C2—C1	120.1 (3)
C15—O2—C16	114.8 (3)	C3—C2—H2	119.9
O1—C1—C2	124.3 (3)	C1—C2—H2	119.9
O1—C1—C6	114.9 (3)	O5—C18—O6	125.4 (4)
C2—C1—C6	120.8 (3)	O5—C18—C17	126.2 (3)
O4—C13—C8	115.2 (3)	O6—C18—C17	108.4 (3)
O4—C13—C12	124.9 (3)	C11—C10—C9	120.6 (4)
C8—C13—C12	119.9 (3)	C11—C10—Cl2	119.4 (3)
C6—C5—C4	120.2 (3)	C9—C10—Cl2	119.9 (3)
C6—C5—H5	119.9	O1—C14—C15	107.4 (3)
C4—C5—H5	119.9	O1—C14—H14A	110.2
C9—C8—C13	119.0 (3)	C15—C14—H14A	110.2
C9—C8—C7	120.9 (3)	O1—C14—H14B	110.2
C13—C8—C7	120.1 (3)	C15—C14—H14B	110.2
C3—C4—C5	121.3 (4)	H14A—C14—H14B	108.5
C3—C4—Cl1	119.4 (3)	C12—C11—C10	119.8 (3)
C5—C4—Cl1	119.3 (3)	C12—C11—H11	120.1
O3—C15—O2	125.2 (4)	C10—C11—H11	120.1
O3—C15—C14	125.8 (3)	C11—C12—C13	120.2 (3)
O2—C15—C14	109.0 (3)	C11—C12—H12	119.9
C5—C6—C1	118.4 (3)	C13—C12—H12	119.9
C5—C6—C7	121.1 (3)	C8—C9—C10	120.6 (3)
C1—C6—C7	120.4 (3)	C8—C9—H9	119.7
O4—C17—C18	108.6 (3)	C10—C9—H9	119.7
O4—C17—H17A	110.0	O6—C19—H19A	109.5
C18—C17—H17A	110.0	O6—C19—H19B	109.5
O4—C17—H17B	110.0	H19A—C19—H19B	109.5
C18—C17—H17B	110.0	O6—C19—H19C	109.5
H17A—C17—H17B	108.3	H19A—C19—H19C	109.5
C6—C7—C8	114.7 (3)	H19B—C19—H19C	109.5

Hydrogen-bond geometry (Å, º)

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 aromatic rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cg1i	0.93	2.72	3.500 (3)	142
C17—H17A···Cg2i	0.97	2.67	3.450 (3)	138

Symmetry code: (i) −x+1, −y+1, −z+2.