Ethyl 4,4''-difluoro-5'-meth-oxy-1,1':3',1''-terphenyl-4'-carboxyl-ate.

In the title compound, C(22)H(18)F(2)O(3), the two fluoro-substituted rings form dihedral angles of 25.89 (15) and 55.00 (12)° with the central benzene ring. The eth-oxy group in the mol-ecule is disordered over two positions with a site-occupancy ratio of 0.662 (7):0.338 (7). In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds into chains along the a axis. The crystal packing is further stabilized by C-H⋯π and π-π inter-actions, with centroid-centroid distances of 3.8605 (15) Å.

Related literature

For a related structure and background to terphenyls, see: Fun et al. (2011 ▶); Samshuddin et al. (2011 ▶). For the synthesis, see: Kotnis (1990 ▶). For reference bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C22H18F2O3

M = 368.36

Orthorhombic,

a = 8.5197 (11) Å

b = 9.5225 (12) Å

c = 22.871 (3) Å

V = 1855.5 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.43 × 0.21 × 0.15 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.958, T max = 0.986

11701 measured reflections

3036 independent reflections

2131 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.171

S = 1.10

3036 reflections

251 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681105344X/rz2682sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681105344X/rz2682Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681105344X/rz2682Isup3.cml

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

C22H18F2O3	F(000) = 768
Mr = 368.36	Dx = 1.319 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3149 reflections
a = 8.5197 (11) Å	θ = 2.3–22.9°
b = 9.5225 (12) Å	µ = 0.10 mm−1
c = 22.871 (3) Å	T = 296 K
V = 1855.5 (4) Å3	Block, colourless
Z = 4	0.43 × 0.21 × 0.15 mm

Bruker APEX DUO CCD area-detector diffractometer	3036 independent reflections
Radiation source: fine-focus sealed tube	2131 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.958, Tmax = 0.986	k = −13→9
11701 measured reflections	l = −26→32

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.171	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0841P)2 + 0.2095P] where P = (Fo2 + 2Fc2)/3
3036 reflections	(Δ/σ)max = 0.011
251 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	−0.2161 (4)	0.4152 (4)	−0.32486 (9)	0.1192 (10)
F2	−0.0906 (3)	−0.0580 (3)	0.15941 (11)	0.1145 (10)
O1	0.2205 (3)	0.7197 (2)	−0.00201 (11)	0.0713 (6)
O2	0.3043 (3)	0.4532 (3)	0.09557 (11)	0.0776 (7)
C1	−0.1600 (4)	0.4267 (5)	−0.26928 (13)	0.0778 (11)
C2	−0.0345 (5)	0.5148 (5)	−0.25967 (14)	0.0806 (11)
H2A	0.0111	0.5650	−0.2901	0.097*
C3	0.0212 (4)	0.5260 (4)	−0.20305 (13)	0.0687 (9)
H3A	0.1063	0.5843	−0.1954	0.082*
C4	−0.0473 (3)	0.4518 (3)	−0.15723 (11)	0.0503 (6)
C5	−0.1719 (3)	0.3640 (3)	−0.16957 (13)	0.0569 (7)
H5A	−0.2183	0.3127	−0.1396	0.068*
C6	−0.2285 (4)	0.3514 (4)	−0.22611 (14)	0.0708 (9)
H6A	−0.3124	0.2920	−0.2343	0.085*
C7	0.0110 (3)	0.4665 (3)	−0.09605 (11)	0.0477 (6)
C8	0.0859 (3)	0.5911 (3)	−0.07870 (12)	0.0524 (6)
H8A	0.0974	0.6644	−0.1052	0.063*
C9	0.1428 (3)	0.6052 (3)	−0.02228 (13)	0.0528 (6)
C10	0.1231 (3)	0.4972 (3)	0.01847 (12)	0.0502 (6)
C11	0.0447 (3)	0.3755 (3)	0.00194 (12)	0.0485 (6)
C12	−0.0081 (3)	0.3612 (3)	−0.05553 (12)	0.0493 (6)
H12A	−0.0574	0.2783	−0.0667	0.059*
C13	0.0119 (3)	0.26039 (16)	0.04462 (8)	0.0530 (6)
C14	−0.0684 (3)	0.28881 (19)	0.09618 (9)	0.0701 (9)
H14A	−0.0987	0.3803	0.1049	0.084*
C15	−0.1035 (3)	0.1805 (3)	0.13478 (8)	0.0852 (11)
H15A	−0.1572	0.1995	0.1693	0.102*
C16	−0.0582 (3)	0.0438 (2)	0.12181 (10)	0.0783 (10)
C17	0.0221 (3)	0.01533 (15)	0.07024 (10)	0.0765 (10)
H17A	0.0524	−0.0762	0.0616	0.092*
C18	0.0571 (3)	0.12364 (19)	0.03165 (8)	0.0649 (8)
H18A	0.1109	0.1046	−0.0029	0.078*
C19	0.1921 (4)	0.5144 (3)	0.07789 (14)	0.0601 (7)
C20	0.2508 (5)	0.8306 (3)	−0.04159 (18)	0.0758 (10)
H20A	0.3045	0.9051	−0.0216	0.114*
H20B	0.1533	0.8653	−0.0570	0.114*
H20C	0.3150	0.7968	−0.0731	0.114*
O3	0.0943 (6)	0.5935 (6)	0.1127 (2)	0.0681 (13)	0.662 (7)
C21	0.1430 (9)	0.6182 (10)	0.1721 (3)	0.101 (2)	0.662 (7)
H21A	0.0502	0.6354	0.1956	0.122*	0.662 (7)
H21B	0.1920	0.5333	0.1868	0.122*	0.662 (7)
C22	0.2433 (17)	0.7258 (11)	0.1799 (5)	0.162 (5)	0.662 (7)
H22A	0.2898	0.7191	0.2181	0.243*	0.662 (7)
H22B	0.1875	0.8130	0.1766	0.243*	0.662 (7)
H22C	0.3241	0.7219	0.1507	0.243*	0.662 (7)
O3X	0.1537 (10)	0.6375 (9)	0.1002 (4)	0.0542 (19)	0.338 (7)
C21X	0.231 (2)	0.674 (2)	0.1527 (5)	0.101 (2)	0.338 (7)
H21C	0.2259	0.7743	0.1595	0.122*	0.338 (7)
H21D	0.3405	0.6455	0.1515	0.122*	0.338 (7)
C22X	0.1341 (17)	0.586 (2)	0.2049 (6)	0.101 (2)	0.338 (7)
H22D	0.1894	0.5948	0.2413	0.152*	0.338 (7)
H22E	0.1269	0.4888	0.1943	0.152*	0.338 (7)
H22F	0.0305	0.6246	0.2090	0.152*	0.338 (7)

	U11	U22	U33	U12	U13	U23
F1	0.1238 (19)	0.184 (3)	0.0495 (10)	−0.031 (2)	−0.0206 (13)	−0.0071 (15)
F2	0.1106 (19)	0.1178 (18)	0.115 (2)	−0.0261 (17)	−0.0049 (16)	0.0635 (17)
O1	0.0911 (15)	0.0529 (12)	0.0699 (13)	−0.0167 (12)	−0.0212 (13)	−0.0061 (11)
O2	0.0827 (15)	0.0703 (13)	0.0798 (15)	0.0215 (13)	−0.0310 (13)	−0.0108 (12)
C1	0.074 (2)	0.114 (3)	0.0449 (15)	−0.001 (2)	−0.0088 (15)	−0.0080 (18)
C2	0.084 (2)	0.107 (3)	0.0504 (17)	−0.017 (2)	0.0000 (16)	0.0070 (18)
C3	0.0666 (18)	0.089 (2)	0.0507 (15)	−0.0189 (18)	−0.0031 (14)	0.0025 (16)
C4	0.0518 (13)	0.0517 (14)	0.0472 (13)	0.0015 (12)	−0.0013 (11)	−0.0051 (12)
C5	0.0565 (14)	0.0635 (17)	0.0508 (15)	−0.0046 (14)	−0.0029 (12)	−0.0042 (13)
C6	0.0681 (18)	0.085 (2)	0.0596 (18)	−0.0133 (18)	−0.0115 (15)	−0.0120 (17)
C7	0.0479 (12)	0.0482 (13)	0.0469 (13)	−0.0001 (11)	−0.0008 (11)	−0.0041 (11)
C8	0.0566 (14)	0.0483 (14)	0.0522 (14)	0.0011 (12)	−0.0040 (12)	0.0003 (12)
C9	0.0550 (13)	0.0480 (15)	0.0553 (15)	−0.0007 (12)	−0.0057 (12)	−0.0081 (12)
C10	0.0521 (13)	0.0463 (13)	0.0522 (14)	0.0074 (11)	−0.0063 (11)	−0.0060 (11)
C11	0.0507 (12)	0.0452 (13)	0.0495 (13)	0.0053 (11)	−0.0055 (11)	−0.0033 (11)
C12	0.0523 (13)	0.0455 (13)	0.0501 (13)	−0.0040 (12)	−0.0024 (11)	−0.0061 (11)
C13	0.0533 (13)	0.0534 (14)	0.0524 (14)	−0.0017 (12)	−0.0082 (12)	0.0002 (12)
C14	0.0736 (19)	0.073 (2)	0.0636 (18)	0.0121 (18)	0.0029 (16)	0.0092 (16)
C15	0.071 (2)	0.119 (3)	0.066 (2)	0.004 (2)	0.0070 (18)	0.017 (2)
C16	0.0675 (18)	0.083 (2)	0.085 (2)	−0.0157 (19)	−0.0109 (18)	0.030 (2)
C17	0.089 (2)	0.0574 (18)	0.083 (2)	−0.0118 (18)	−0.013 (2)	0.0115 (17)
C18	0.0804 (19)	0.0503 (15)	0.0639 (18)	−0.0037 (15)	−0.0085 (16)	0.0022 (14)
C19	0.0694 (17)	0.0488 (15)	0.0621 (17)	0.0097 (14)	−0.0164 (14)	−0.0082 (13)
C20	0.084 (2)	0.0539 (17)	0.090 (2)	−0.0160 (17)	−0.009 (2)	−0.0042 (17)
O3	0.067 (3)	0.088 (3)	0.049 (2)	0.010 (2)	−0.006 (2)	−0.020 (2)
C21	0.093 (3)	0.159 (7)	0.053 (3)	0.015 (4)	−0.010 (3)	−0.033 (4)
C22	0.229 (13)	0.114 (7)	0.142 (9)	−0.014 (8)	−0.090 (9)	−0.010 (6)
O3X	0.054 (4)	0.059 (4)	0.049 (4)	0.004 (3)	−0.003 (3)	−0.004 (3)
C21X	0.093 (3)	0.159 (7)	0.053 (3)	0.015 (4)	−0.010 (3)	−0.033 (4)
C22X	0.093 (3)	0.159 (7)	0.053 (3)	0.015 (4)	−0.010 (3)	−0.033 (4)

F1—C1	1.362 (4)	C14—C15	1.3900
F2—C16	1.325 (3)	C14—H14A	0.9300
O1—C9	1.357 (3)	C15—C16	1.3900
O1—C20	1.415 (4)	C15—H15A	0.9300
O2—C19	1.191 (4)	C16—C17	1.3900
C1—C6	1.353 (5)	C17—C18	1.3900
C1—C2	1.376 (5)	C17—H17A	0.9300
C2—C3	1.383 (5)	C18—H18A	0.9300
C2—H2A	0.9300	C19—O3X	1.320 (9)
C3—C4	1.392 (4)	C19—O3	1.377 (5)
C3—H3A	0.9300	C20—H20A	0.9600
C4—C5	1.381 (4)	C20—H20B	0.9600
C4—C7	1.491 (4)	C20—H20C	0.9600
C5—C6	1.385 (4)	O3—C21	1.440 (8)
C5—H5A	0.9300	C21—C22	1.346 (14)
C6—H6A	0.9300	C21—H21A	0.9700
C7—C12	1.375 (4)	C21—H21B	0.9700
C7—C8	1.404 (4)	C22—H22A	0.9600
C8—C9	1.385 (4)	C22—H22B	0.9600
C8—H8A	0.9300	C22—H22C	0.9600
C9—C10	1.398 (4)	O3X—C21X	1.414 (16)
C10—C11	1.390 (4)	C21X—C22X	1.68 (3)
C10—C19	1.490 (4)	C21X—H21C	0.9700
C11—C12	1.396 (4)	C21X—H21D	0.9700
C11—C13	1.494 (3)	C22X—H22D	0.9600
C12—H12A	0.9300	C22X—H22E	0.9600
C13—C14	1.3900	C22X—H22F	0.9600
C13—C18	1.3900
C9—O1—C20	118.0 (2)	C16—C15—C14	120.0
C6—C1—F1	119.2 (3)	C16—C15—H15A	120.0
C6—C1—C2	122.8 (3)	C14—C15—H15A	120.0
F1—C1—C2	118.0 (3)	F2—C16—C17	120.7 (2)
C1—C2—C3	117.6 (3)	F2—C16—C15	119.3 (2)
C1—C2—H2A	121.2	C17—C16—C15	120.0
C3—C2—H2A	121.2	C16—C17—C18	120.0
C2—C3—C4	121.5 (3)	C16—C17—H17A	120.0
C2—C3—H3A	119.3	C18—C17—H17A	120.0
C4—C3—H3A	119.3	C17—C18—C13	120.0
C5—C4—C3	118.4 (3)	C17—C18—H18A	120.0
C5—C4—C7	120.3 (3)	C13—C18—H18A	120.0
C3—C4—C7	121.3 (3)	O2—C19—O3X	120.2 (5)
C6—C5—C4	120.7 (3)	O2—C19—O3	123.9 (3)
C6—C5—H5A	119.6	O2—C19—C10	125.0 (3)
C4—C5—H5A	119.6	O3X—C19—C10	110.6 (4)
C1—C6—C5	119.0 (3)	O3—C19—C10	110.4 (3)
C1—C6—H6A	120.5	O1—C20—H20A	109.5
C5—C6—H6A	120.5	O1—C20—H20B	109.5
C12—C7—C8	118.6 (2)	H20A—C20—H20B	109.5
C12—C7—C4	121.6 (2)	O1—C20—H20C	109.5
C8—C7—C4	119.7 (2)	H20A—C20—H20C	109.5
C9—C8—C7	120.3 (3)	H20B—C20—H20C	109.5
C9—C8—H8A	119.9	C19—O3—C21	117.4 (5)
C7—C8—H8A	119.9	C22—C21—O3	115.7 (10)
O1—C9—C8	124.6 (3)	C22—C21—H21A	108.4
O1—C9—C10	114.9 (2)	O3—C21—H21A	108.4
C8—C9—C10	120.5 (3)	C22—C21—H21B	108.4
C11—C10—C9	119.3 (2)	O3—C21—H21B	108.4
C11—C10—C19	122.0 (2)	H21A—C21—H21B	107.4
C9—C10—C19	118.7 (2)	C19—O3X—C21X	115.5 (10)
C10—C11—C12	119.5 (2)	O3X—C21X—C22X	104.7 (15)
C10—C11—C13	121.6 (2)	O3X—C21X—H21C	110.8
C12—C11—C13	118.9 (2)	C22X—C21X—H21C	110.8
C7—C12—C11	121.7 (2)	O3X—C21X—H21D	110.8
C7—C12—H12A	119.2	C22X—C21X—H21D	110.8
C11—C12—H12A	119.2	H21C—C21X—H21D	108.9
C14—C13—C18	120.0	C21X—C22X—H22D	109.5
C14—C13—C11	120.24 (15)	C21X—C22X—H22E	109.5
C18—C13—C11	119.72 (15)	H22D—C22X—H22E	109.5
C13—C14—C15	120.0	C21X—C22X—H22F	109.5
C13—C14—H14A	120.0	H22D—C22X—H22F	109.5
C15—C14—H14A	120.0	H22E—C22X—H22F	109.5
C6—C1—C2—C3	−0.5 (6)	C10—C11—C12—C7	−2.1 (4)
F1—C1—C2—C3	179.9 (4)	C13—C11—C12—C7	176.5 (2)
C1—C2—C3—C4	−0.4 (6)	C10—C11—C13—C14	55.1 (3)
C2—C3—C4—C5	1.1 (5)	C12—C11—C13—C14	−123.4 (2)
C2—C3—C4—C7	−178.7 (3)	C10—C11—C13—C18	−127.1 (2)
C3—C4—C5—C6	−0.8 (5)	C12—C11—C13—C18	54.4 (3)
C7—C4—C5—C6	178.9 (3)	C18—C13—C14—C15	0.0
F1—C1—C6—C5	−179.6 (4)	C11—C13—C14—C15	177.8 (2)
C2—C1—C6—C5	0.7 (6)	C13—C14—C15—C16	0.0
C4—C5—C6—C1	−0.1 (6)	C14—C15—C16—F2	179.1 (2)
C5—C4—C7—C12	26.1 (4)	C14—C15—C16—C17	0.0
C3—C4—C7—C12	−154.1 (3)	F2—C16—C17—C18	−179.1 (2)
C5—C4—C7—C8	−153.1 (3)	C15—C16—C17—C18	0.0
C3—C4—C7—C8	26.6 (4)	C16—C17—C18—C13	0.0
C12—C7—C8—C9	1.7 (4)	C14—C13—C18—C17	0.0
C4—C7—C8—C9	−179.0 (2)	C11—C13—C18—C17	−177.8 (2)
C20—O1—C9—C8	−2.3 (5)	C11—C10—C19—O2	70.4 (4)
C20—O1—C9—C10	177.3 (3)	C9—C10—C19—O2	−107.4 (4)
C7—C8—C9—O1	178.1 (3)	C11—C10—C19—O3X	−132.9 (5)
C7—C8—C9—C10	−1.5 (4)	C9—C10—C19—O3X	49.3 (6)
O1—C9—C10—C11	179.9 (2)	C11—C10—C19—O3	−100.0 (4)
C8—C9—C10—C11	−0.4 (4)	C9—C10—C19—O3	82.2 (4)
O1—C9—C10—C19	−2.2 (4)	O2—C19—O3—C21	8.6 (9)
C8—C9—C10—C19	177.4 (3)	O3X—C19—O3—C21	−84.6 (11)
C9—C10—C11—C12	2.2 (4)	C10—C19—O3—C21	179.1 (6)
C19—C10—C11—C12	−175.6 (3)	C19—O3—C21—C22	83.5 (10)
C9—C10—C11—C13	−176.3 (2)	O2—C19—O3X—C21X	−13.1 (13)
C19—C10—C11—C13	5.9 (4)	O3—C19—O3X—C21X	93.4 (14)
C8—C7—C12—C11	0.1 (4)	C10—C19—O3X—C21X	−171.1 (10)
C4—C7—C12—C11	−179.2 (2)	C19—O3X—C21X—C22X	−79.9 (12)

Cg2 and Cg3 are the centroids of the C7–C12 and C13–C18 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2i	0.93	2.59	3.515 (3)	179.
C5—H5A···Cg3ii	0.93	2.92	3.589 (3)	130
C20—H20A···Cg2iii	0.96	2.83	3.710 (4)	152

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the C7–C12 and C13–C18 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O2i	0.93	2.59	3.515 (3)	179
C5—H5A⋯Cg3ii	0.93	2.92	3.589 (3)	130
C20—H20A⋯Cg2iii	0.96	2.83	3.710 (4)	152

Symmetry codes: (i) ; (ii) ; (iii) .