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

In the title compound, C(21)H(16)F(2)O(3), the pendant fluoro-benzene rings form dihedral angles of 22.22 (12) and 50.74 (11)° with the central benzene ring. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds into chains along the a axis. The crystal structure also features C-H⋯π inter-actions.

Related literature

For a related structure and background to terphenyls, see: Fun et al. (2011 ▶). For further related structures, see: Betz et al. (2011a ▶,b ▶). For further synthetic details, see: Kotnis (1990 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For reference bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C21H16F2O3

M = 354.34

Orthorhombic,

a = 8.1270 (1) Å

b = 9.4681 (1) Å

c = 22.3297 (3) Å

V = 1718.21 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.26 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.973, T max = 0.982

11903 measured reflections

2851 independent reflections

2411 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.102

S = 1.13

2851 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.51 e Å−3

Δρmin = −0.28 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/S1600536811048719/hb6516sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048719/hb6516Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811048719/hb6516Isup3.cml

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

C21H16F2O3	F(000) = 736
Mr = 354.34	Dx = 1.370 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3629 reflections
a = 8.1270 (1) Å	θ = 2.8–30.6°
b = 9.4681 (1) Å	µ = 0.11 mm−1
c = 22.3297 (3) Å	T = 100 K
V = 1718.21 (4) Å3	Block, colourless
Z = 4	0.26 × 0.20 × 0.18 mm

Bruker SMART APEXII CCD diffractometer	2851 independent reflections
Radiation source: fine-focus sealed tube	2411 reflections with I > 2σ(I)
graphite	Rint = 0.043
φ and ω scans	θmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→9
Tmin = 0.973, Tmax = 0.982	k = −13→10
11903 measured reflections	l = −31→30

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0345P)2 + 0.548P] where P = (Fo2 + 2Fc2)/3
2851 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
F1	0.7209 (2)	0.59514 (17)	0.82984 (6)	0.0346 (4)
F2	0.5985 (2)	1.05766 (16)	0.32763 (7)	0.0340 (4)
O1	0.2900 (2)	0.27202 (16)	0.49542 (7)	0.0214 (4)
O2	0.1948 (2)	0.54018 (18)	0.39484 (7)	0.0252 (4)
O3	0.3970 (2)	0.38062 (19)	0.38201 (7)	0.0264 (4)
C1	0.6798 (3)	0.6457 (2)	0.66999 (10)	0.0182 (5)
H1A	0.7260	0.7022	0.6391	0.022*
C2	0.7354 (3)	0.6627 (3)	0.72845 (10)	0.0218 (5)
H2A	0.8180	0.7301	0.7379	0.026*
C3	0.6670 (3)	0.5787 (3)	0.77222 (10)	0.0223 (5)
C4	0.5468 (4)	0.4812 (3)	0.76107 (10)	0.0260 (6)
H4A	0.5018	0.4255	0.7924	0.031*
C5	0.4921 (3)	0.4661 (3)	0.70215 (10)	0.0234 (5)
H5A	0.4087	0.3990	0.6934	0.028*
C6	0.5580 (3)	0.5481 (2)	0.65562 (9)	0.0163 (4)
C7	0.4997 (3)	0.5310 (2)	0.59270 (9)	0.0155 (4)
C8	0.4251 (3)	0.4044 (2)	0.57459 (9)	0.0173 (5)
H8A	0.4136	0.3287	0.6022	0.021*
C9	0.3682 (3)	0.3896 (2)	0.51633 (10)	0.0160 (4)
C10	0.3870 (3)	0.4985 (2)	0.47469 (9)	0.0160 (4)
C11	0.4653 (3)	0.6234 (2)	0.49160 (9)	0.0153 (4)
C12	0.5185 (3)	0.6392 (2)	0.55078 (10)	0.0162 (4)
H12A	0.5686	0.7254	0.5627	0.019*
C13	0.4995 (3)	0.7377 (2)	0.44754 (10)	0.0162 (4)
C14	0.5776 (3)	0.7085 (2)	0.39312 (10)	0.0202 (5)
H14A	0.6068	0.6140	0.3836	0.024*
C15	0.6131 (3)	0.8163 (3)	0.35290 (11)	0.0236 (5)
H15A	0.6665	0.7966	0.3160	0.028*
C16	0.5690 (3)	0.9521 (3)	0.36781 (11)	0.0234 (5)
C17	0.4933 (3)	0.9866 (2)	0.42104 (11)	0.0223 (5)
H17A	0.4643	1.0815	0.4300	0.027*
C18	0.4605 (3)	0.8777 (2)	0.46129 (10)	0.0202 (5)
H18A	0.4109	0.8990	0.4987	0.024*
C19	0.2657 (3)	0.1589 (2)	0.53712 (10)	0.0207 (5)
H19A	0.2153	0.0784	0.5165	0.031*
H19B	0.1932	0.1906	0.5695	0.031*
H19C	0.3721	0.1303	0.5539	0.031*
C20	0.3146 (3)	0.4776 (2)	0.41326 (10)	0.0181 (5)
C21	0.3284 (4)	0.3466 (4)	0.32363 (12)	0.0410 (8)
H21A	0.2347	0.2825	0.3286	0.062*
H21B	0.4127	0.3009	0.2990	0.062*
H21C	0.2915	0.4336	0.3040	0.062*

	U11	U22	U33	U12	U13	U23
F1	0.0421 (10)	0.0490 (10)	0.0127 (7)	−0.0089 (8)	−0.0074 (7)	−0.0038 (7)
F2	0.0373 (10)	0.0306 (8)	0.0341 (8)	−0.0019 (8)	0.0038 (8)	0.0178 (7)
O1	0.0310 (10)	0.0176 (7)	0.0157 (7)	−0.0079 (7)	−0.0028 (7)	0.0001 (6)
O2	0.0299 (10)	0.0233 (8)	0.0224 (8)	0.0058 (8)	−0.0088 (8)	−0.0020 (7)
O3	0.0301 (10)	0.0354 (10)	0.0137 (8)	0.0092 (8)	−0.0040 (7)	−0.0068 (7)
C1	0.0211 (12)	0.0182 (10)	0.0152 (10)	−0.0020 (10)	0.0016 (9)	−0.0008 (8)
C2	0.0232 (13)	0.0239 (11)	0.0184 (11)	−0.0035 (10)	−0.0031 (10)	−0.0035 (9)
C3	0.0268 (13)	0.0292 (12)	0.0109 (10)	0.0017 (11)	−0.0042 (10)	−0.0036 (9)
C4	0.0308 (15)	0.0330 (13)	0.0141 (10)	−0.0048 (12)	0.0007 (10)	0.0033 (10)
C5	0.0255 (13)	0.0292 (12)	0.0154 (10)	−0.0076 (11)	−0.0023 (10)	0.0014 (10)
C6	0.0182 (11)	0.0182 (10)	0.0125 (9)	0.0006 (9)	0.0000 (9)	−0.0017 (8)
C7	0.0140 (10)	0.0183 (10)	0.0141 (10)	0.0009 (9)	−0.0003 (9)	−0.0016 (8)
C8	0.0198 (12)	0.0184 (10)	0.0136 (10)	−0.0010 (9)	0.0007 (9)	0.0021 (8)
C9	0.0162 (11)	0.0156 (9)	0.0161 (10)	−0.0006 (8)	−0.0016 (9)	−0.0012 (8)
C10	0.0167 (11)	0.0176 (10)	0.0136 (9)	0.0021 (8)	0.0004 (9)	−0.0013 (8)
C11	0.0158 (11)	0.0147 (9)	0.0154 (10)	0.0022 (8)	0.0012 (9)	0.0000 (8)
C12	0.0172 (11)	0.0168 (10)	0.0146 (10)	−0.0001 (9)	−0.0005 (9)	−0.0017 (8)
C13	0.0158 (11)	0.0176 (10)	0.0151 (10)	−0.0007 (9)	−0.0025 (9)	0.0013 (8)
C14	0.0203 (12)	0.0210 (11)	0.0192 (10)	0.0012 (10)	−0.0026 (10)	0.0018 (9)
C15	0.0223 (13)	0.0302 (13)	0.0183 (11)	−0.0001 (10)	0.0016 (10)	0.0048 (10)
C16	0.0230 (13)	0.0229 (11)	0.0244 (12)	−0.0037 (10)	−0.0019 (10)	0.0106 (10)
C17	0.0253 (13)	0.0161 (10)	0.0255 (12)	−0.0011 (10)	−0.0048 (11)	0.0027 (9)
C18	0.0252 (13)	0.0176 (10)	0.0179 (11)	−0.0003 (9)	−0.0027 (10)	0.0001 (9)
C19	0.0237 (13)	0.0189 (10)	0.0197 (11)	−0.0042 (10)	−0.0022 (10)	0.0009 (9)
C20	0.0222 (12)	0.0158 (10)	0.0163 (10)	−0.0024 (9)	−0.0002 (9)	0.0014 (8)
C21	0.052 (2)	0.0546 (18)	0.0166 (12)	0.0205 (17)	−0.0117 (13)	−0.0164 (13)

F1—C3	1.368 (3)	C9—C10	1.397 (3)
F2—C16	1.364 (3)	C10—C11	1.395 (3)
O1—C9	1.364 (3)	C10—C20	1.506 (3)
O1—C19	1.433 (3)	C11—C12	1.398 (3)
O2—C20	1.211 (3)	C11—C13	1.489 (3)
O3—C20	1.334 (3)	C12—H12A	0.9500
O3—C21	1.454 (3)	C13—C18	1.397 (3)
C1—C2	1.391 (3)	C13—C14	1.399 (3)
C1—C6	1.392 (3)	C14—C15	1.390 (3)
C1—H1A	0.9500	C14—H14A	0.9500
C2—C3	1.377 (3)	C15—C16	1.376 (3)
C2—H2A	0.9500	C15—H15A	0.9500
C3—C4	1.367 (4)	C16—C17	1.378 (3)
C4—C5	1.396 (3)	C17—C18	1.393 (3)
C4—H4A	0.9500	C17—H17A	0.9500
C5—C6	1.403 (3)	C18—H18A	0.9500
C5—H5A	0.9500	C19—H19A	0.9800
C6—C7	1.491 (3)	C19—H19B	0.9800
C7—C12	1.396 (3)	C19—H19C	0.9800
C7—C8	1.403 (3)	C21—H21A	0.9800
C8—C9	1.388 (3)	C21—H21B	0.9800
C8—H8A	0.9500	C21—H21C	0.9800
C9—O1—C19	116.85 (17)	C7—C12—H12A	119.3
C20—O3—C21	115.4 (2)	C11—C12—H12A	119.3
C2—C1—C6	121.6 (2)	C18—C13—C14	118.8 (2)
C2—C1—H1A	119.2	C18—C13—C11	120.1 (2)
C6—C1—H1A	119.2	C14—C13—C11	121.00 (19)
C3—C2—C1	117.9 (2)	C15—C14—C13	120.7 (2)
C3—C2—H2A	121.0	C15—C14—H14A	119.7
C1—C2—H2A	121.0	C13—C14—H14A	119.7
C4—C3—F1	118.5 (2)	C16—C15—C14	118.4 (2)
C4—C3—C2	123.3 (2)	C16—C15—H15A	120.8
F1—C3—C2	118.2 (2)	C14—C15—H15A	120.8
C3—C4—C5	117.9 (2)	F2—C16—C15	118.7 (2)
C3—C4—H4A	121.0	F2—C16—C17	118.2 (2)
C5—C4—H4A	121.0	C15—C16—C17	123.1 (2)
C4—C5—C6	121.3 (2)	C16—C17—C18	117.8 (2)
C4—C5—H5A	119.3	C16—C17—H17A	121.1
C6—C5—H5A	119.3	C18—C17—H17A	121.1
C1—C6—C5	117.9 (2)	C17—C18—C13	121.1 (2)
C1—C6—C7	121.0 (2)	C17—C18—H18A	119.4
C5—C6—C7	121.1 (2)	C13—C18—H18A	119.4
C12—C7—C8	118.75 (19)	O1—C19—H19A	109.5
C12—C7—C6	121.2 (2)	O1—C19—H19B	109.5
C8—C7—C6	120.1 (2)	H19A—C19—H19B	109.5
C9—C8—C7	120.0 (2)	O1—C19—H19C	109.5
C9—C8—H8A	120.0	H19A—C19—H19C	109.5
C7—C8—H8A	120.0	H19B—C19—H19C	109.5
O1—C9—C8	124.0 (2)	O2—C20—O3	124.2 (2)
O1—C9—C10	115.18 (18)	O2—C20—C10	124.0 (2)
C8—C9—C10	120.9 (2)	O3—C20—C10	111.8 (2)
C9—C10—C11	119.69 (19)	O3—C21—H21A	109.5
C9—C10—C20	117.84 (19)	O3—C21—H21B	109.5
C11—C10—C20	122.42 (19)	H21A—C21—H21B	109.5
C10—C11—C12	119.20 (19)	O3—C21—H21C	109.5
C10—C11—C13	121.49 (19)	H21A—C21—H21C	109.5
C12—C11—C13	119.26 (19)	H21B—C21—H21C	109.5
C7—C12—C11	121.4 (2)
C6—C1—C2—C3	0.5 (4)	C9—C10—C11—C13	175.2 (2)
C1—C2—C3—C4	−0.7 (4)	C20—C10—C11—C13	−7.3 (3)
C1—C2—C3—F1	−179.9 (2)	C8—C7—C12—C11	−0.2 (4)
F1—C3—C4—C5	179.6 (2)	C6—C7—C12—C11	179.5 (2)
C2—C3—C4—C5	0.4 (4)	C10—C11—C12—C7	2.1 (3)
C3—C4—C5—C6	0.0 (4)	C13—C11—C12—C7	−175.4 (2)
C2—C1—C6—C5	−0.1 (4)	C10—C11—C13—C18	132.5 (2)
C2—C1—C6—C7	−179.9 (2)	C12—C11—C13—C18	−50.0 (3)
C4—C5—C6—C1	−0.2 (4)	C10—C11—C13—C14	−50.5 (3)
C4—C5—C6—C7	179.7 (2)	C12—C11—C13—C14	127.0 (2)
C1—C6—C7—C12	−22.6 (3)	C18—C13—C14—C15	−1.3 (4)
C5—C6—C7—C12	157.5 (2)	C11—C13—C14—C15	−178.3 (2)
C1—C6—C7—C8	157.1 (2)	C13—C14—C15—C16	−0.2 (4)
C5—C6—C7—C8	−22.8 (3)	C14—C15—C16—F2	−177.8 (2)
C12—C7—C8—C9	−1.5 (3)	C14—C15—C16—C17	0.8 (4)
C6—C7—C8—C9	178.8 (2)	F2—C16—C17—C18	178.7 (2)
C19—O1—C9—C8	0.4 (3)	C15—C16—C17—C18	0.0 (4)
C19—O1—C9—C10	−178.9 (2)	C16—C17—C18—C13	−1.6 (4)
C7—C8—C9—O1	−178.0 (2)	C14—C13—C18—C17	2.2 (4)
C7—C8—C9—C10	1.3 (4)	C11—C13—C18—C17	179.2 (2)
O1—C9—C10—C11	179.9 (2)	C21—O3—C20—O2	−3.3 (3)
C8—C9—C10—C11	0.6 (3)	C21—O3—C20—C10	175.9 (2)
O1—C9—C10—C20	2.4 (3)	C9—C10—C20—O2	108.9 (3)
C8—C9—C10—C20	−177.0 (2)	C11—C10—C20—O2	−68.6 (3)
C9—C10—C11—C12	−2.3 (3)	C9—C10—C20—O3	−70.2 (3)
C20—C10—C11—C12	175.2 (2)	C11—C10—C20—O3	112.3 (2)

Cg1 and Cg2 are the centroids of the C13—C18 and C7–C12 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2i	0.95	2.57	3.310 (3)	135
C1—H1A···Cg1ii	0.95	2.76	3.367 (3)	123
C19—H19A···Cg2iii	0.98	2.62	3.466 (2)	144

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C13—C18 and C7–C12 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O2i	0.95	2.57	3.310 (3)	135
C1—H1A⋯Cg1ii	0.95	2.76	3.367 (3)	123
C19—H19A⋯Cg2iii	0.98	2.62	3.466 (2)	144

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