5-(5-Bromo-2-meth­oxy­phen­yl)-2-fluoro­pyridine

In the title compound, C₁₂H₉BrFNO, the dihedral angle between the aromatic rings is 51.39 (5)°; the C atom of the meth­oxy group is close to being coplanar with its attached ring (r.m.s. deviation = 0.0172 Å] and is oriented away from the pyridine ring. In the crystal, mol­ecules inter­act by van der Waals forces.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.035
• wR factor = 0.068
• Data-to-parameter ratio = 13.9

checkCIF/PLATON results

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Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   1 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
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S1. Comment

We have reported the crystal structure of 5-(4-chlorophenyl)-2-fluoropyridine (Adeel et al., 2012), 4-(2-fluoropyridin-5-yl)phenol (Elahi et al., 2012a), 5-(2,3-dichlorophenyl)-2-fluoropyridine (Elahi et al., 2012b) and 2-fluoro-5-(4-fluorophenyl)pyridine (Elahi et al., 2012) which have common moiety of 2-fluoropyridine as in the title compound, (Fig. 1).

In the title compound, the 1-bromo-4-methoxybenzene A (C1–C7/BR1/O1) and the 2-fluoropyridine B (C8—C12/N1/F1) systems are almost planar with r.m.s. deviations of 0.0172 Å and 0.0087 Å, respectively. The dihedral angle between A/B is 51.39 (5)°. There does not exist any kind of H-bonding and the molecules interact by van der Waals forces.

Related literature

For a related structure, see: Adeel et al. (2012); Elahi et al. (2012a,b); Elahi et al. (2012).

S2. Experimental

To a 6 ml solution of 5-bromo-2-fluoropyridine (0.20 g, 1.13 mmol), 5-bromo-2-methoxyphenylboronic acid (0.314 g, 1.36 mmol) in dioxane and K₃PO₄ (0.361 g, 1.7 mmol, in 1 ml H₂O) was added Pd(PPh₃)₄ (1.5 mole %) at 373 K under N₂ atmosphere. The reaction mixture was refluxed for 8 h. Then 20 ml of distilled water was added. The aqueous layer was extracted three times with EtOAc(3 × 15 ml). The organic layer was evaporated in vacuo and the crude product was obtained. Colorless needles of (I) were obtained by the recrystalization of crude product in a saturated CHCl₃/CH₃OH solution.

Yield: 0.294 g, 92%. m.p. 345–347 K.

S3. Refinement

The H-atoms were positioned geometrically (C–H = 0.93–0.96 Å) and refined as riding with U_iso(H) = xU_eq(C), where x = 1.5 for methyl and x = 1.2 for other H-atoms.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures

Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.

5-(5-Bromo-2-methoxyphenyl)-2-fluoropyridine

Crystal data

C12H9BrFNO	F(000) = 560
Mr = 282.11	Dx = 1.714 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1441 reflections
a = 3.9376 (4) Å	θ = 1.8–25.5°
b = 20.999 (3) Å	µ = 3.75 mm^−1
c = 13.2700 (15) Å	T = 296 K
β = 95.035 (7)°	Needle, colorless
V = 1093.0 (2) Å^3	0.34 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer	2027 independent reflections
Radiation source: fine-focus sealed tube	1441 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 8.10 pixels mm^-1	θmax = 25.5°, θmin = 1.8°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −25→15
Tmin = 0.674, Tmax = 0.698	l = −15→16
7773 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.027P)^2] where P = (Fo^2 + 2Fc^2)/3
2027 reflections	(Δ/σ)max = 0.001
146 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

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

	x	y	z	Uiso*/Ueq
Br1	0.56028 (8)	0.42649 (2)	0.65535 (3)	0.0533 (1)
F1	0.6238 (6)	0.43194 (10)	−0.01878 (15)	0.0815 (9)
O1	1.0021 (5)	0.25300 (10)	0.32894 (14)	0.0422 (7)
N1	0.5368 (7)	0.35827 (13)	0.0979 (2)	0.0501 (11)
C1	0.7736 (7)	0.35084 (13)	0.3789 (2)	0.0326 (10)
C2	0.9046 (7)	0.29045 (14)	0.4060 (2)	0.0337 (10)
C3	0.9321 (7)	0.27195 (15)	0.5063 (2)	0.0407 (11)
C4	0.8285 (7)	0.31185 (16)	0.5803 (3)	0.0439 (11)
C5	0.7032 (7)	0.37101 (14)	0.5544 (2)	0.0377 (11)
C6	0.6760 (7)	0.39044 (14)	0.4547 (2)	0.0378 (10)
C7	1.1517 (8)	0.19256 (15)	0.3560 (3)	0.0511 (12)
C8	0.7416 (7)	0.37357 (13)	0.2724 (2)	0.0333 (10)
C9	0.8664 (7)	0.43295 (15)	0.2473 (2)	0.0429 (11)
C10	0.8273 (8)	0.45436 (16)	0.1482 (3)	0.0510 (11)
C11	0.6638 (9)	0.41379 (17)	0.0803 (3)	0.0516 (12)
C12	0.5761 (7)	0.33878 (15)	0.1936 (2)	0.0418 (11)
H3	1.02142	0.23212	0.52415	0.0488*
H4	0.84380	0.29866	0.64746	0.0525*
H6	0.59073	0.43076	0.43811	0.0454*
H7A	1.23508	0.17326	0.29741	0.0763*
H7B	0.98311	0.16542	0.38171	0.0763*
H7C	1.33727	0.19847	0.40709	0.0763*
H9	0.97674	0.45841	0.29733	0.0514*
H10	0.90758	0.49388	0.12940	0.0611*
H12	0.48683	0.29927	0.20876	0.0503*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0574 (2)	0.0553 (2)	0.0484 (2)	−0.0061 (2)	0.0108 (2)	−0.0154 (2)
F1	0.138 (2)	0.0654 (14)	0.0405 (13)	0.0176 (14)	0.0042 (12)	0.0153 (12)
O1	0.0590 (13)	0.0327 (12)	0.0339 (13)	0.0100 (11)	−0.0007 (10)	0.0006 (11)
N1	0.0724 (19)	0.0421 (18)	0.0340 (18)	0.0103 (16)	−0.0060 (14)	0.0015 (15)
C1	0.0329 (16)	0.0309 (17)	0.0330 (19)	−0.0033 (14)	−0.0023 (14)	0.0005 (15)
C2	0.0343 (16)	0.0343 (17)	0.0316 (19)	−0.0043 (15)	−0.0022 (14)	−0.0027 (16)
C3	0.0501 (18)	0.0339 (18)	0.037 (2)	−0.0014 (16)	−0.0026 (15)	0.0062 (16)
C4	0.0507 (19)	0.048 (2)	0.0316 (19)	−0.0100 (17)	−0.0040 (15)	0.0046 (17)
C5	0.0379 (17)	0.0410 (19)	0.034 (2)	−0.0041 (15)	0.0014 (14)	−0.0062 (16)
C6	0.0371 (17)	0.0322 (17)	0.043 (2)	−0.0003 (15)	−0.0025 (14)	−0.0026 (17)
C7	0.059 (2)	0.040 (2)	0.053 (2)	0.0107 (17)	−0.0028 (17)	−0.0056 (18)
C8	0.0343 (16)	0.0294 (17)	0.0362 (19)	0.0064 (14)	0.0028 (14)	0.0004 (15)
C9	0.0474 (18)	0.0372 (19)	0.043 (2)	−0.0009 (16)	−0.0016 (15)	−0.0009 (18)
C10	0.065 (2)	0.0376 (19)	0.051 (2)	0.0003 (18)	0.0087 (18)	0.0078 (19)
C11	0.071 (2)	0.050 (2)	0.034 (2)	0.021 (2)	0.0063 (17)	0.0084 (19)
C12	0.0521 (19)	0.0320 (18)	0.040 (2)	0.0030 (16)	−0.0033 (16)	−0.0003 (17)

Geometric parameters (Å, º)

Br1—C5	1.898 (3)	C8—C9	1.391 (4)
F1—C11	1.365 (4)	C8—C12	1.390 (4)
O1—C2	1.371 (3)	C9—C10	1.386 (5)
O1—C7	1.432 (4)	C10—C11	1.360 (5)
N1—C11	1.298 (5)	C3—H3	0.9300
N1—C12	1.330 (4)	C4—H4	0.9300
C1—C2	1.404 (4)	C6—H6	0.9300
C1—C6	1.385 (4)	C7—H7A	0.9600
C1—C8	1.487 (4)	C7—H7B	0.9600
C2—C3	1.382 (4)	C7—H7C	0.9600
C3—C4	1.380 (5)	C9—H9	0.9300
C4—C5	1.369 (4)	C10—H10	0.9300
C5—C6	1.380 (4)	C12—H12	0.9300
C2—O1—C7	117.2 (2)	N1—C11—C10	127.7 (4)
C11—N1—C12	115.7 (3)	N1—C12—C8	124.3 (3)
C2—C1—C6	118.4 (2)	C2—C3—H3	120.00
C2—C1—C8	122.2 (2)	C4—C3—H3	120.00
C6—C1—C8	119.5 (2)	C3—C4—H4	120.00
O1—C2—C1	116.6 (2)	C5—C4—H4	120.00
O1—C2—C3	123.6 (3)	C1—C6—H6	119.00
C1—C2—C3	119.8 (3)	C5—C6—H6	119.00
C2—C3—C4	120.8 (3)	O1—C7—H7A	109.00
C3—C4—C5	119.7 (3)	O1—C7—H7B	109.00
Br1—C5—C4	120.2 (2)	O1—C7—H7C	109.00
Br1—C5—C6	119.5 (2)	H7A—C7—H7B	109.00
C4—C5—C6	120.3 (3)	H7A—C7—H7C	109.00
C1—C6—C5	121.0 (3)	H7B—C7—H7C	109.00
C1—C8—C9	120.9 (2)	C8—C9—H9	120.00
C1—C8—C12	122.8 (2)	C10—C9—H9	120.00
C9—C8—C12	116.3 (2)	C9—C10—H10	122.00
C8—C9—C10	120.4 (3)	C11—C10—H10	122.00
C9—C10—C11	115.6 (3)	N1—C12—H12	118.00
F1—C11—N1	114.2 (3)	C8—C12—H12	118.00
F1—C11—C10	118.1 (3)
C7—O1—C2—C1	177.0 (2)	O1—C2—C3—C4	−179.8 (3)
C7—O1—C2—C3	−2.4 (4)	C1—C2—C3—C4	0.8 (4)
C12—N1—C11—F1	179.1 (3)	C2—C3—C4—C5	−1.3 (4)
C12—N1—C11—C10	−0.9 (5)	C3—C4—C5—Br1	−179.9 (2)
C11—N1—C12—C8	−0.3 (5)	C3—C4—C5—C6	0.9 (4)
C6—C1—C2—O1	−179.2 (2)	Br1—C5—C6—C1	−179.1 (2)
C6—C1—C2—C3	0.2 (4)	C4—C5—C6—C1	0.1 (4)
C8—C1—C2—O1	−0.1 (4)	C1—C8—C9—C10	−178.3 (3)
C8—C1—C2—C3	179.3 (3)	C12—C8—C9—C10	−0.8 (4)
C2—C1—C6—C5	−0.6 (4)	C1—C8—C12—N1	178.6 (3)
C8—C1—C6—C5	−179.8 (3)	C9—C8—C12—N1	1.1 (4)
C2—C1—C8—C9	−130.1 (3)	C8—C9—C10—C11	−0.2 (4)
C2—C1—C8—C12	52.6 (4)	C9—C10—C11—F1	−178.8 (3)
C6—C1—C8—C9	49.0 (4)	C9—C10—C11—N1	1.2 (5)
C6—C1—C8—C12	−128.3 (3)