Intricacies of ligand coordination in tricarbonylchromium(0) complexes with ortho- and para-fluoro­biphenyls

The steric and electronic factors that influence which of the two rings of a substituted biphenyl ligand coordinates to chromium are of interest and it has been suggested that haptotropic rearrangements within these mol­ecules may be limited if the arene–arene dihedral angle is too large. Two tricarbonylchromium(0) complexes and their respective free ligands have been characterized by single-crystal X-ray diffraction. In the solid state, tricarbon­yl[(1′,2′,3′,4′,5′,6′-η)-2-fluoro-1,1′-biphen­yl]chromium(0), [Cr(C₁₂H₉F)(CO)₃], (I), exists as the more stable isomer with the non­halogenated arene ring ligated to the metal center. Similarly, tricarbon­yl[(1′,2′,3′,4′,5′,6′-η)-4-fluoro-1,1′-biphen­yl]chromium(0) crys­tallizes as the more stable isomer with the phenyl ring bonded to the Cr⁰ center. The arene–arene dihedral angles in these complexes are 55.77 (4) and 52.4 (5)°, respectively. Structural features of these complexes are compared to those of the DFT-optimized geometries of ten tricarbon­yl[(η⁶-C₆H₅)(4-F-C₆H₄)]chromium model complexes. The solid-state structures of the free ligands 2-fluoro-1,1′-biphenyl and 4-fluoro-1,1′-biphenyl, both C₁₂H₉F, exhibit arene–arene dihedral angles of 54.83 (7) and 0.71 (8)°, respectively. The mol­ecules of the free ligands occupy crystallographic twofold axes and exhibit positional disorder. Weak inter­molecular C—H...F inter­actions are observed in all four structures.

Computing details

Data collection: SMART (Bruker, 2003) for cze005, czerwinski10; APEX3 (Bruker, 2016) for czerwinski13, czerwinski12. Cell refinement: SAINT (Bruker, 2003) for cze005, czerwinski10; SAINT-Plus (Bruker, 2016) for czerwinski13, czerwinski12. Data reduction: SAINT (Bruker, 2003) for cze005, czerwinski10; SAINT-Plus (Bruker, 2016) for czerwinski13, czerwinski12. Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for cze005, czerwinski10; SHELXT (Sheldrick, 2015a) for czerwinski13, czerwinski12. Program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b) for cze005, czerwinski13, czerwinski12; SHELXL2016 (Sheldrick, 2015a) for czerwinski10. For all structures, molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Tricarbonyl[(1',2',3',4',5',6'-η)-2-fluoro-1,1'-biphenyl]chromium(0) (cze005)

Crystal data

[Cr(C12H9F)(CO)3]	F(000) = 624
Mr = 308.22	Dx = 1.632 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.0166 (3) Å	Cell parameters from 13200 reflections
b = 27.4725 (11) Å	θ = 3.0–26.4°
c = 7.1101 (3) Å	µ = 0.93 mm^−1
β = 113.738 (1)°	T = 100 K
V = 1254.61 (9) Å^3	Plate, yellow
Z = 4	0.4 × 0.34 × 0.14 mm

Data collection

Bruker SAINT CCD area detector diffractometer	2421 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
phi and ω scans	θmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
Tmin = 0.708, Tmax = 0.881	k = −34→34
20790 measured reflections	l = −8→8
2571 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 0.6955P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.003
2571 reflections	Δρmax = 0.39 e Å^−3
181 parameters	Δρmin = −0.20 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cr1	0.25461 (3)	0.58849 (2)	0.64906 (3)	0.01547 (9)
F1	0.37666 (14)	0.73489 (3)	1.07416 (15)	0.0279 (2)
O1	0.49510 (17)	0.63961 (4)	0.44226 (17)	0.0293 (3)
O2	0.5439 (2)	0.50310 (5)	0.7360 (2)	0.0413 (3)
O3	−0.01617 (19)	0.54368 (4)	0.24436 (17)	0.0300 (3)
C1	0.3565 (2)	0.64130 (5)	0.9095 (2)	0.0167 (3)
C2	0.3366 (2)	0.59475 (5)	0.9828 (2)	0.0190 (3)
H2	0.450980	0.580891	1.093855	0.023*
C3	0.1477 (2)	0.56839 (5)	0.8924 (2)	0.0222 (3)
H3	0.135100	0.537237	0.944280	0.027*
C4	−0.0201 (2)	0.58829 (5)	0.7269 (2)	0.0227 (3)
H4	−0.146121	0.570447	0.665358	0.027*
C5	−0.0027 (2)	0.63495 (5)	0.6505 (2)	0.0208 (3)
H5	−0.117514	0.648641	0.539334	0.025*
C6	0.1848 (2)	0.66086 (5)	0.7399 (2)	0.0180 (3)
H6	0.197228	0.691839	0.686547	0.022*
C7	0.5553 (2)	0.66864 (5)	1.0082 (2)	0.0170 (3)
C8	0.5598 (2)	0.71474 (5)	1.0896 (2)	0.0198 (3)
C9	0.7405 (2)	0.74085 (6)	1.1899 (2)	0.0235 (3)
H9	0.736754	0.772398	1.243049	0.028*
C10	0.9282 (2)	0.71984 (6)	1.2113 (2)	0.0236 (3)
H10	1.054849	0.736997	1.280648	0.028*
C11	0.9313 (2)	0.67377 (6)	1.1317 (2)	0.0227 (3)
H11	1.059841	0.659598	1.145747	0.027*
C12	0.7465 (2)	0.64847 (5)	1.0315 (2)	0.0202 (3)
H12	0.750021	0.616957	0.977952	0.024*
C13	0.4037 (2)	0.61937 (5)	0.5220 (2)	0.0196 (3)
C14	0.4319 (3)	0.53577 (6)	0.7022 (2)	0.0259 (3)
C15	0.0890 (2)	0.56070 (5)	0.3997 (2)	0.0207 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.01797 (14)	0.01454 (13)	0.01487 (13)	−0.00037 (8)	0.00763 (10)	−0.00078 (7)
F1	0.0240 (5)	0.0243 (5)	0.0340 (5)	0.0041 (4)	0.0101 (4)	−0.0087 (4)
O1	0.0245 (6)	0.0416 (7)	0.0245 (6)	−0.0076 (5)	0.0128 (5)	0.0009 (5)
O2	0.0579 (9)	0.0349 (7)	0.0359 (7)	0.0255 (6)	0.0240 (6)	0.0107 (5)
O3	0.0370 (6)	0.0274 (6)	0.0234 (6)	−0.0101 (5)	0.0098 (5)	−0.0077 (5)
C1	0.0194 (7)	0.0161 (6)	0.0168 (6)	0.0003 (5)	0.0097 (5)	−0.0024 (5)
C2	0.0258 (7)	0.0187 (7)	0.0146 (6)	0.0000 (5)	0.0103 (6)	−0.0013 (5)
C3	0.0315 (8)	0.0196 (7)	0.0214 (7)	−0.0052 (6)	0.0169 (6)	−0.0028 (6)
C4	0.0216 (7)	0.0266 (8)	0.0239 (7)	−0.0072 (6)	0.0133 (6)	−0.0073 (6)
C5	0.0174 (7)	0.0251 (7)	0.0212 (7)	0.0013 (5)	0.0090 (6)	−0.0037 (6)
C6	0.0199 (7)	0.0158 (6)	0.0201 (7)	0.0017 (5)	0.0100 (6)	−0.0011 (5)
C7	0.0191 (7)	0.0174 (7)	0.0141 (6)	−0.0005 (5)	0.0062 (5)	0.0012 (5)
C8	0.0205 (7)	0.0199 (7)	0.0187 (7)	0.0028 (5)	0.0074 (6)	0.0001 (5)
C9	0.0291 (8)	0.0192 (7)	0.0200 (7)	−0.0039 (6)	0.0076 (6)	−0.0016 (6)
C10	0.0222 (7)	0.0270 (8)	0.0173 (7)	−0.0069 (6)	0.0034 (6)	0.0023 (6)
C11	0.0183 (7)	0.0287 (8)	0.0198 (7)	0.0020 (6)	0.0062 (6)	0.0057 (6)
C12	0.0227 (7)	0.0197 (7)	0.0182 (7)	0.0028 (6)	0.0084 (6)	0.0022 (5)
C13	0.0169 (6)	0.0237 (7)	0.0161 (6)	0.0009 (5)	0.0044 (5)	−0.0025 (5)
C14	0.0363 (8)	0.0246 (8)	0.0197 (7)	0.0056 (7)	0.0142 (6)	0.0024 (6)
C15	0.0252 (7)	0.0173 (7)	0.0228 (7)	−0.0023 (6)	0.0128 (6)	0.0003 (6)

Geometric parameters (Å, º)

Cr1—C1	2.2311 (14)	C3—H3	0.9500
Cr1—C2	2.2115 (14)	C3—C4	1.398 (2)
Cr1—C3	2.2150 (14)	C4—H4	0.9500
Cr1—C4	2.2087 (15)	C4—C5	1.416 (2)
Cr1—C5	2.2146 (14)	C5—H5	0.9500
Cr1—C6	2.2056 (14)	C5—C6	1.403 (2)
Cr1—C13	1.8415 (15)	C6—H6	0.9500
Cr1—C14	1.8466 (16)	C7—C8	1.387 (2)
Cr1—C15	1.8487 (15)	C7—C12	1.398 (2)
F1—C8	1.3622 (17)	C8—C9	1.380 (2)
O1—C13	1.1552 (19)	C9—H9	0.9500
O2—C14	1.153 (2)	C9—C10	1.389 (2)
O3—C15	1.1521 (19)	C10—H10	0.9500
C1—C2	1.409 (2)	C10—C11	1.390 (2)
C1—C6	1.423 (2)	C11—H11	0.9500
C1—C7	1.4882 (19)	C11—C12	1.388 (2)
C2—H2	0.9500	C12—H12	0.9500
C2—C3	1.417 (2)
C2—Cr1—C1	36.98 (5)	C3—C2—H2	119.7
C2—Cr1—C3	37.34 (5)	Cr1—C3—H3	129.9
C2—Cr1—C5	79.09 (6)	C2—C3—Cr1	71.19 (8)
C3—Cr1—C1	67.04 (5)	C2—C3—H3	120.0
C4—Cr1—C1	79.29 (5)	C4—C3—Cr1	71.33 (9)
C4—Cr1—C2	66.91 (6)	C4—C3—C2	119.91 (13)
C4—Cr1—C3	36.84 (6)	C4—C3—H3	120.0
C4—Cr1—C5	37.35 (6)	Cr1—C4—H4	129.1
C5—Cr1—C1	67.09 (5)	C3—C4—Cr1	71.82 (9)
C5—Cr1—C3	66.85 (6)	C3—C4—H4	119.9
C6—Cr1—C1	37.40 (5)	C3—C4—C5	120.23 (14)
C6—Cr1—C2	66.94 (5)	C5—C4—Cr1	71.55 (8)
C6—Cr1—C3	79.11 (5)	C5—C4—H4	119.9
C6—Cr1—C4	67.03 (5)	Cr1—C5—H5	130.1
C6—Cr1—C5	37.01 (5)	C4—C5—Cr1	71.10 (9)
C13—Cr1—C1	92.99 (6)	C4—C5—H5	120.2
C13—Cr1—C2	122.46 (6)	C6—C5—Cr1	71.15 (8)
C13—Cr1—C3	159.39 (6)	C6—C5—C4	119.68 (14)
C13—Cr1—C4	148.14 (6)	C6—C5—H5	120.2
C13—Cr1—C5	111.23 (6)	Cr1—C6—H6	128.6
C13—Cr1—C6	88.02 (6)	C1—C6—Cr1	72.27 (8)
C13—Cr1—C14	89.58 (7)	C1—C6—H6	119.6
C13—Cr1—C15	88.96 (6)	C5—C6—Cr1	71.85 (8)
C14—Cr1—C1	112.08 (6)	C5—C6—C1	120.79 (13)
C14—Cr1—C2	88.78 (6)	C5—C6—H6	119.6
C14—Cr1—C3	93.25 (6)	C8—C7—C1	121.13 (13)
C14—Cr1—C4	122.05 (7)	C8—C7—C12	116.92 (13)
C14—Cr1—C5	159.15 (6)	C12—C7—C1	121.89 (12)
C14—Cr1—C6	149.09 (6)	F1—C8—C7	118.36 (13)
C14—Cr1—C15	89.08 (7)	F1—C8—C9	118.12 (13)
C15—Cr1—C1	158.75 (6)	C9—C8—C7	123.50 (14)
C15—Cr1—C2	148.48 (6)	C8—C9—H9	120.8
C15—Cr1—C3	111.48 (6)	C8—C9—C10	118.30 (14)
C15—Cr1—C4	87.93 (6)	C10—C9—H9	120.8
C15—Cr1—C5	92.49 (6)	C9—C10—H10	119.9
C15—Cr1—C6	121.67 (6)	C9—C10—C11	120.23 (14)
C2—C1—Cr1	70.76 (8)	C11—C10—H10	119.9
C2—C1—C6	118.70 (13)	C10—C11—H11	120.0
C2—C1—C7	119.80 (13)	C12—C11—C10	120.01 (14)
C6—C1—Cr1	70.33 (8)	C12—C11—H11	120.0
C6—C1—C7	121.49 (12)	C7—C12—H12	119.5
C7—C1—Cr1	130.24 (9)	C11—C12—C7	121.04 (14)
Cr1—C2—H2	129.0	C11—C12—H12	119.5
C1—C2—Cr1	72.27 (8)	O1—C13—Cr1	178.60 (13)
C1—C2—H2	119.7	O2—C14—Cr1	179.46 (17)
C1—C2—C3	120.66 (14)	O3—C15—Cr1	179.23 (14)
C3—C2—Cr1	71.46 (8)
Cr1—C1—C2—C3	−54.72 (12)	C3—C4—C5—Cr1	54.90 (13)
Cr1—C1—C6—C5	55.16 (12)	C3—C4—C5—C6	0.9 (2)
Cr1—C1—C7—C8	147.56 (12)	C4—C5—C6—Cr1	53.94 (12)
Cr1—C1—C7—C12	−35.26 (19)	C4—C5—C6—C1	−1.4 (2)
Cr1—C2—C3—C4	−54.13 (12)	C6—C1—C2—Cr1	53.30 (11)
Cr1—C3—C4—C5	−54.77 (13)	C6—C1—C2—C3	−1.4 (2)
Cr1—C4—C5—C6	−53.96 (12)	C6—C1—C7—C8	57.48 (19)
Cr1—C5—C6—C1	−55.36 (12)	C6—C1—C7—C12	−125.33 (15)
F1—C8—C9—C10	178.12 (13)	C7—C1—C2—Cr1	−126.06 (12)
C1—C2—C3—Cr1	55.10 (12)	C7—C1—C2—C3	179.22 (13)
C1—C2—C3—C4	1.0 (2)	C7—C1—C6—Cr1	125.84 (12)
C1—C7—C8—F1	−1.0 (2)	C7—C1—C6—C5	−179.00 (13)
C1—C7—C8—C9	177.32 (14)	C7—C8—C9—C10	−0.2 (2)
C1—C7—C12—C11	−177.31 (13)	C8—C7—C12—C11	0.0 (2)
C2—C1—C6—Cr1	−53.50 (11)	C8—C9—C10—C11	0.4 (2)
C2—C1—C6—C5	1.7 (2)	C9—C10—C11—C12	−0.4 (2)
C2—C1—C7—C8	−123.18 (15)	C10—C11—C12—C7	0.2 (2)
C2—C1—C7—C12	54.00 (19)	C12—C7—C8—F1	−178.32 (12)
C2—C3—C4—Cr1	54.06 (12)	C12—C7—C8—C9	0.0 (2)
C2—C3—C4—C5	−0.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···F1^i	0.95	2.66	3.5612 (17)	158
C10—H10···F1^ii	0.95	2.50	3.4013 (17)	158

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x+1, −y+3/2, z+1/2.

Tricarbonyl[(1',2',3',4',5',6'-η)-4-fluoro-1,1'-biphenyl]chromium(0) (czerwinski10)

Crystal data

[Cr(C12H9F)(CO)3]	F(000) = 624
Mr = 308.22	Dx = 1.590 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 7.0616 (5) Å	Cell parameters from 9875 reflections
b = 28.3503 (19) Å	θ = 3.1–71.7°
c = 7.0571 (4) Å	µ = 7.48 mm^−1
β = 114.324 (5)°	T = 120 K
V = 1287.40 (15) Å^3	Block, yellow
Z = 4	0.66 × 0.31 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer	2479 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
φ and ω scans	θmax = 72.4°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
Tmin = 0.083, Tmax = 0.381	k = −34→33
19716 measured reflections	l = −8→8
2520 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 0.8185P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
2520 reflections	Δρmax = 0.30 e Å^−3
181 parameters	Δρmin = −0.39 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cr1	0.24469 (4)	0.08560 (2)	0.14453 (4)	0.01430 (10)
F1	1.0904 (2)	0.23850 (5)	0.7983 (2)	0.0457 (4)
O1	0.4870 (2)	0.13494 (5)	−0.0586 (2)	0.0305 (3)
O2	0.5257 (3)	0.00166 (6)	0.2294 (2)	0.0453 (4)
O3	−0.0315 (2)	0.04327 (5)	−0.2657 (2)	0.0306 (3)
C1	0.3515 (3)	0.13767 (6)	0.4048 (2)	0.0159 (3)
C2	0.3381 (3)	0.09256 (6)	0.4825 (3)	0.0191 (3)
H2	0.455869	0.079641	0.593405	0.023*
C3	0.1510 (3)	0.06625 (6)	0.3973 (3)	0.0231 (4)
H3	0.143228	0.036093	0.452306	0.028*
C4	−0.0218 (3)	0.08472 (6)	0.2324 (3)	0.0250 (4)
H4	−0.146809	0.066977	0.174633	0.030*
C5	−0.0115 (3)	0.12983 (6)	0.1507 (3)	0.0222 (4)
H5	−0.129418	0.142450	0.038919	0.027*
C6	0.1743 (3)	0.15576 (6)	0.2360 (3)	0.0182 (3)
H6	0.181558	0.185846	0.180030	0.022*
C7	0.5471 (3)	0.16526 (6)	0.4991 (2)	0.0165 (3)
C8	0.5428 (3)	0.21124 (6)	0.5691 (3)	0.0228 (4)
H8	0.413670	0.225397	0.547814	0.027*
C9	0.7261 (3)	0.23633 (7)	0.6694 (3)	0.0289 (4)
H9	0.724466	0.267531	0.717834	0.035*
C10	0.9098 (3)	0.21487 (7)	0.6967 (3)	0.0274 (4)
C11	0.9208 (3)	0.16984 (7)	0.6270 (3)	0.0257 (4)
H11	1.050455	0.156221	0.646503	0.031*
C12	0.7369 (3)	0.14524 (6)	0.5279 (3)	0.0206 (3)
H12	0.740333	0.114189	0.478782	0.025*
C13	0.3950 (3)	0.11531 (6)	0.0192 (2)	0.0190 (3)
C14	0.4165 (3)	0.03381 (7)	0.1955 (3)	0.0259 (4)
C15	0.0753 (3)	0.05941 (6)	−0.1081 (3)	0.0207 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.02042 (17)	0.01303 (16)	0.01223 (16)	−0.00087 (9)	0.00954 (12)	−0.00134 (9)
F1	0.0372 (7)	0.0362 (7)	0.0445 (7)	−0.0186 (6)	−0.0026 (6)	0.0048 (6)
O1	0.0274 (7)	0.0454 (8)	0.0234 (7)	−0.0098 (6)	0.0153 (6)	0.0014 (6)
O2	0.0717 (11)	0.0378 (8)	0.0347 (8)	0.0311 (8)	0.0301 (8)	0.0127 (6)
O3	0.0417 (8)	0.0275 (7)	0.0212 (7)	−0.0131 (6)	0.0116 (6)	−0.0081 (5)
C1	0.0234 (8)	0.0145 (7)	0.0140 (7)	0.0003 (6)	0.0118 (7)	−0.0032 (6)
C2	0.0304 (9)	0.0169 (8)	0.0135 (8)	−0.0011 (7)	0.0127 (7)	−0.0013 (6)
C3	0.0379 (10)	0.0199 (8)	0.0216 (8)	−0.0069 (7)	0.0223 (8)	−0.0047 (7)
C4	0.0279 (10)	0.0282 (9)	0.0276 (10)	−0.0094 (7)	0.0201 (8)	−0.0095 (7)
C5	0.0206 (8)	0.0265 (9)	0.0233 (9)	0.0010 (7)	0.0129 (7)	−0.0055 (7)
C6	0.0233 (8)	0.0152 (7)	0.0204 (8)	0.0028 (6)	0.0135 (7)	−0.0023 (6)
C7	0.0242 (8)	0.0143 (7)	0.0117 (7)	−0.0008 (6)	0.0082 (6)	0.0000 (6)
C8	0.0289 (9)	0.0168 (8)	0.0206 (8)	0.0013 (7)	0.0082 (7)	−0.0027 (7)
C9	0.0412 (11)	0.0161 (8)	0.0244 (9)	−0.0054 (7)	0.0086 (8)	−0.0022 (7)
C10	0.0281 (10)	0.0262 (9)	0.0190 (9)	−0.0108 (8)	0.0006 (7)	0.0048 (7)
C11	0.0237 (9)	0.0285 (9)	0.0216 (9)	0.0002 (7)	0.0061 (7)	0.0066 (7)
C12	0.0260 (9)	0.0181 (8)	0.0179 (8)	0.0018 (7)	0.0091 (7)	0.0006 (6)
C13	0.0187 (8)	0.0240 (8)	0.0136 (7)	−0.0004 (7)	0.0058 (6)	−0.0036 (6)
C14	0.0420 (11)	0.0239 (9)	0.0164 (8)	0.0075 (8)	0.0165 (8)	0.0030 (7)
C15	0.0291 (9)	0.0158 (8)	0.0217 (9)	−0.0041 (7)	0.0150 (7)	−0.0004 (7)

Geometric parameters (Å, º)

Cr1—C1	2.2316 (15)	C3—H3	0.9500
Cr1—C2	2.2061 (17)	C3—C4	1.395 (3)
Cr1—C3	2.2118 (16)	C4—H4	0.9500
Cr1—C4	2.2104 (18)	C4—C5	1.417 (3)
Cr1—C5	2.2160 (17)	C5—H5	0.9500
Cr1—C6	2.2102 (16)	C5—C6	1.405 (2)
Cr1—C13	1.8417 (17)	C6—H6	0.9500
Cr1—C14	1.8432 (19)	C7—C8	1.399 (2)
Cr1—C15	1.8448 (18)	C7—C12	1.391 (2)
F1—C10	1.355 (2)	C8—H8	0.9500
O1—C13	1.152 (2)	C8—C9	1.389 (3)
O2—C14	1.154 (2)	C9—H9	0.9500
O3—C15	1.151 (2)	C9—C10	1.373 (3)
C1—C2	1.410 (2)	C10—C11	1.382 (3)
C1—C6	1.422 (2)	C11—H11	0.9500
C1—C7	1.485 (2)	C11—C12	1.383 (3)
C2—H2	0.9500	C12—H12	0.9500
C2—C3	1.417 (3)
C2—Cr1—C1	37.05 (6)	C3—C2—H2	119.6
C2—Cr1—C3	37.42 (7)	Cr1—C3—H3	129.8
C2—Cr1—C4	66.90 (7)	C2—C3—Cr1	71.07 (9)
C2—Cr1—C5	79.11 (7)	C2—C3—H3	120.1
C2—Cr1—C6	66.85 (6)	C4—C3—Cr1	71.55 (10)
C3—Cr1—C1	67.19 (6)	C4—C3—C2	119.89 (16)
C3—Cr1—C5	66.85 (7)	C4—C3—H3	120.1
C4—Cr1—C1	79.33 (6)	Cr1—C4—H4	129.3
C4—Cr1—C3	36.79 (8)	C3—C4—Cr1	71.66 (10)
C4—Cr1—C5	37.34 (7)	C3—C4—H4	119.9
C5—Cr1—C1	67.15 (6)	C3—C4—C5	120.29 (17)
C6—Cr1—C1	37.33 (6)	C5—C4—Cr1	71.55 (10)
C6—Cr1—C3	79.03 (6)	C5—C4—H4	119.9
C6—Cr1—C4	66.95 (6)	Cr1—C5—H5	129.8
C6—Cr1—C5	37.01 (6)	C4—C5—Cr1	71.12 (10)
C13—Cr1—C1	91.52 (7)	C4—C5—H5	120.2
C13—Cr1—C2	120.24 (7)	C6—C5—Cr1	71.27 (9)
C13—Cr1—C3	157.48 (7)	C6—C5—C4	119.56 (17)
C13—Cr1—C4	149.93 (7)	C6—C5—H5	120.2
C13—Cr1—C5	112.78 (7)	Cr1—C6—H6	129.0
C13—Cr1—C6	88.41 (7)	C1—C6—Cr1	72.15 (9)
C13—Cr1—C14	89.70 (8)	C1—C6—H6	119.5
C13—Cr1—C15	89.56 (7)	C5—C6—Cr1	71.72 (10)
C14—Cr1—C1	113.21 (7)	C5—C6—C1	120.98 (15)
C14—Cr1—C2	88.90 (7)	C5—C6—H6	119.5
C14—Cr1—C3	92.09 (7)	C8—C7—C1	119.86 (15)
C14—Cr1—C4	120.27 (8)	C12—C7—C1	120.85 (14)
C14—Cr1—C5	157.49 (8)	C12—C7—C8	119.22 (16)
C14—Cr1—C6	150.36 (8)	C7—C8—H8	119.8
C14—Cr1—C15	88.88 (8)	C9—C8—C7	120.42 (17)
C15—Cr1—C1	157.89 (7)	C9—C8—H8	119.8
C15—Cr1—C2	150.09 (7)	C8—C9—H9	120.9
C15—Cr1—C3	112.91 (7)	C10—C9—C8	118.24 (17)
C15—Cr1—C4	88.78 (7)	C10—C9—H9	120.9
C15—Cr1—C5	92.13 (7)	F1—C10—C9	118.94 (18)
C15—Cr1—C6	120.68 (7)	F1—C10—C11	117.83 (18)
C2—C1—Cr1	70.49 (9)	C9—C10—C11	123.23 (17)
C2—C1—C6	118.43 (15)	C10—C11—H11	121.1
C2—C1—C7	120.19 (15)	C10—C11—C12	117.86 (17)
C6—C1—Cr1	70.52 (9)	C12—C11—H11	121.1
C6—C1—C7	121.38 (14)	C7—C12—H12	119.5
C7—C1—Cr1	130.85 (11)	C11—C12—C7	121.02 (16)
Cr1—C2—H2	128.8	C11—C12—H12	119.5
C1—C2—Cr1	72.46 (9)	O1—C13—Cr1	178.29 (16)
C1—C2—H2	119.6	O2—C14—Cr1	179.2 (2)
C1—C2—C3	120.84 (16)	O3—C15—Cr1	179.48 (18)
C3—C2—Cr1	71.51 (10)
Cr1—C1—C2—C3	−54.82 (14)	C3—C4—C5—Cr1	54.62 (15)
Cr1—C1—C6—C5	54.72 (14)	C3—C4—C5—C6	0.4 (2)
Cr1—C1—C7—C8	144.23 (14)	C4—C5—C6—Cr1	54.18 (14)
Cr1—C1—C7—C12	−38.8 (2)	C4—C5—C6—C1	−0.7 (2)
Cr1—C2—C3—C4	−54.34 (14)	C6—C1—C2—Cr1	53.55 (13)
Cr1—C3—C4—C5	−54.56 (15)	C6—C1—C2—C3	−1.3 (2)
Cr1—C4—C5—C6	−54.26 (14)	C6—C1—C7—C8	53.6 (2)
Cr1—C5—C6—C1	−54.92 (13)	C6—C1—C7—C12	−129.43 (17)
F1—C10—C11—C12	178.40 (16)	C7—C1—C2—Cr1	−126.63 (14)
C1—C2—C3—Cr1	55.26 (14)	C7—C1—C2—C3	178.55 (14)
C1—C2—C3—C4	0.9 (2)	C7—C1—C6—Cr1	126.65 (14)
C1—C7—C8—C9	175.90 (16)	C7—C1—C6—C5	−178.63 (14)
C1—C7—C12—C11	−176.06 (15)	C7—C8—C9—C10	0.3 (3)
C2—C1—C6—Cr1	−53.54 (13)	C8—C7—C12—C11	0.9 (2)
C2—C1—C6—C5	1.2 (2)	C8—C9—C10—F1	−178.58 (17)
C2—C1—C7—C8	−126.21 (17)	C8—C9—C10—C11	0.9 (3)
C2—C1—C7—C12	50.8 (2)	C9—C10—C11—C12	−1.1 (3)
C2—C3—C4—Cr1	54.12 (14)	C10—C11—C12—C7	0.1 (3)
C2—C3—C4—C5	−0.4 (3)	C12—C7—C8—C9	−1.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···F1^i	0.95	2.48	3.122 (2)	125
C8—H8···F1^i	0.95	2.46	3.295 (2)	147

Symmetry code: (i) x−1, −y+1/2, z−1/2.

4-Fluoro-1,1'-biphenyl (czerwinski13)

Crystal data

C12H9F	Dx = 1.328 Mg m^−3
Mr = 172.19	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Fdd2	Cell parameters from 5876 reflections
a = 12.9824 (9) Å	θ = 7.7–72.8°
b = 23.0588 (15) Å	µ = 0.74 mm^−1
c = 5.7527 (4) Å	T = 100 K
V = 1722.1 (2) Å^3	Needle, colourless
Z = 8	0.56 × 0.14 × 0.02 mm
F(000) = 720

Data collection

Bruker SMART APEXII diffractometer	836 independent reflections
Radiation source: sealed X-ray tube, Siemens, K FFCU 2K 90	825 reflections with I > 2σ(I)
Equatorially mounted graphite monochromator	Rint = 0.028
Detector resolution: 7.9 pixels mm^-1	θmax = 72.8°, θmin = 7.7°
0.60° ω and 0.6° φ scans	h = −15→15
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −28→28
Tmin = 0.671, Tmax = 0.754	l = −7→7
7085 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0611P)^2 + 2.1311P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.107	(Δ/σ)max < 0.001
S = 1.13	Δρmax = 0.36 e Å^−3
836 reflections	Δρmin = −0.16 e Å^−3
64 parameters	Absolute structure: Flack x determined using 351 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.07 (17)
Primary atom site location: dual

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	0.5021 (2)	0.56162 (12)	0.7706 (5)	0.0335 (8)	0.5
C1	0.54787 (16)	0.51796 (9)	0.4167 (4)	0.0223 (6)
C2	0.57037 (17)	0.55520 (10)	0.6000 (4)	0.0244 (6)
H2	0.524692	0.556868	0.728848	0.029*	0.5
C3	0.65725 (19)	0.58986 (10)	0.6001 (5)	0.0277 (6)
H3	0.670501	0.615208	0.726828	0.033*
C4	0.72528 (19)	0.58731 (10)	0.4129 (4)	0.0280 (6)
H4	0.784987	0.611122	0.410672	0.034*
C5	0.70540 (18)	0.54998 (10)	0.2306 (5)	0.0277 (6)
H5	0.752322	0.547626	0.104202	0.033*
C6	0.61707 (18)	0.51579 (10)	0.2308 (4)	0.0247 (6)
H6	0.603680	0.490710	0.103350	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0373 (16)	0.0363 (15)	0.0268 (16)	−0.0006 (12)	0.0046 (12)	−0.0015 (13)
C1	0.0202 (10)	0.0220 (11)	0.0247 (14)	0.0034 (9)	−0.0026 (9)	0.0043 (9)
C2	0.0245 (11)	0.0258 (12)	0.0228 (14)	0.0037 (9)	0.0003 (10)	0.0001 (10)
C3	0.0301 (13)	0.0259 (11)	0.0272 (13)	−0.0006 (9)	−0.0054 (11)	0.0003 (10)
C4	0.0228 (11)	0.0272 (11)	0.0340 (14)	−0.0019 (9)	−0.0032 (10)	0.0047 (11)
C5	0.0227 (11)	0.0327 (12)	0.0278 (13)	0.0019 (9)	0.0015 (10)	0.0056 (11)
C6	0.0247 (11)	0.0264 (11)	0.0229 (12)	0.0027 (9)	0.0001 (10)	−0.0007 (9)

Geometric parameters (Å, º)

F1—C2	1.331 (4)	C3—C4	1.394 (4)
C1—C1^i	1.494 (4)	C4—H4	0.9500
C1—C2	1.391 (3)	C4—C5	1.381 (4)
C1—C6	1.397 (3)	C5—H5	0.9500
C2—H2	0.9500	C5—C6	1.392 (4)
C2—C3	1.382 (3)	C6—H6	0.9500
C3—H3	0.9500
C2—C1—C1^i	121.13 (16)	C4—C3—H3	120.3
C2—C1—C6	117.9 (2)	C3—C4—H4	120.2
C6—C1—C1^i	121.01 (17)	C5—C4—C3	119.6 (2)
F1—C2—C1	119.2 (2)	C5—C4—H4	120.2
F1—C2—C3	118.6 (2)	C4—C5—H5	119.8
C1—C2—H2	119.0	C4—C5—C6	120.4 (2)
C3—C2—C1	121.9 (2)	C6—C5—H5	119.8
C3—C2—H2	119.0	C1—C6—H6	119.7
C2—C3—H3	120.3	C5—C6—C1	120.7 (2)
C2—C3—C4	119.5 (2)	C5—C6—H6	119.7
F1—C2—C3—C4	−174.6 (2)	C2—C3—C4—C5	−0.4 (3)
C1^i—C1—C2—F1	−4.4 (4)	C3—C4—C5—C6	1.2 (4)
C1^i—C1—C2—C3	−178.3 (2)	C4—C5—C6—C1	−1.0 (4)
C1^i—C1—C6—C5	179.1 (2)	C6—C1—C2—F1	174.8 (2)
C1—C2—C3—C4	−0.6 (3)	C6—C1—C2—C3	0.9 (3)
C2—C1—C6—C5	−0.1 (3)

Symmetry code: (i) −x+1, −y+1, z.

2-Fluoro-1,1'-biphenyl (czerwinski12)

Crystal data

C12H9F	Dx = 1.339 Mg m^−3
Mr = 172.19	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 6339 reflections
a = 5.6462 (14) Å	θ = 3.4–28.3°
b = 20.739 (5) Å	µ = 0.09 mm^−1
c = 7.292 (2) Å	T = 100 K
V = 853.9 (4) Å^3	Needle, colourless
Z = 4	0.39 × 0.11 × 0.03 mm
F(000) = 360

Data collection

Bruker APEXII Quazar diffractometer	1055 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	899 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.029
Detector resolution: 7.9 pixels mm^-1	θmax = 28.3°, θmin = 2.0°
0.5° ω and 0.5° φ scans	h = −7→7
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −27→27
Tmin = 0.706, Tmax = 0.746	l = −9→9
19177 measured reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.0828P)^2 + 0.1921P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
1055 reflections	Δρmax = 0.45 e Å^−3
68 parameters	Δρmin = −0.16 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	0.500000	0.95466 (5)	0.250000	0.0291 (4)	0.789 (2)
F2	0.500000	0.48895 (18)	0.250000	0.0321 (12)	0.211 (2)
C1	0.500000	0.89062 (7)	0.250000	0.0218 (3)
H1	0.499999	0.936429	0.249997	0.026*	0.211 (2)
C2	0.31493 (18)	0.85859 (5)	0.33221 (14)	0.0241 (3)
H2	0.189391	0.881754	0.388628	0.029*
C3	0.31572 (17)	0.79142 (5)	0.33088 (13)	0.0217 (3)
H3	0.187996	0.768828	0.386240	0.026*
C4	0.500000	0.75641 (6)	0.250000	0.0161 (3)
C5	0.500000	0.68428 (7)	0.250000	0.0166 (3)
C6	0.31769 (18)	0.64928 (5)	0.33289 (14)	0.0247 (3)
H6	0.191342	0.671769	0.390424	0.030*
C7	0.3172 (2)	0.58230 (6)	0.33300 (15)	0.0280 (3)
H7	0.191316	0.559467	0.390068	0.034*
C8	0.500000	0.54887 (7)	0.250000	0.0258 (4)
H8	0.499999	0.503065	0.250001	0.031*	0.789 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0344 (7)	0.0153 (6)	0.0376 (7)	0.000	0.0039 (5)	0.000
F2	0.039 (2)	0.0129 (19)	0.045 (3)	0.000	0.006 (2)	0.000
C1	0.0233 (7)	0.0219 (7)	0.0200 (7)	0.000	−0.0026 (5)	0.000
C2	0.0215 (6)	0.0255 (6)	0.0253 (5)	0.0067 (4)	0.0048 (4)	0.0030 (4)
C3	0.0174 (5)	0.0247 (6)	0.0229 (5)	0.0024 (4)	0.0050 (4)	0.0056 (4)
C4	0.0140 (6)	0.0221 (7)	0.0122 (6)	0.000	−0.0016 (4)	0.000
C5	0.0147 (6)	0.0221 (7)	0.0131 (6)	0.000	−0.0012 (5)	0.000
C6	0.0213 (5)	0.0245 (6)	0.0281 (6)	−0.0038 (4)	0.0075 (4)	−0.0067 (4)
C7	0.0269 (6)	0.0252 (6)	0.0319 (6)	−0.0085 (4)	0.0078 (4)	−0.0044 (4)
C8	0.0296 (8)	0.0218 (7)	0.0259 (7)	0.000	−0.0002 (6)	0.000

Geometric parameters (Å, º)

F1—C1	1.3280 (17)	C4—C5	1.4959 (19)
F2—C8	1.243 (4)	C5—C6	1.3971 (12)
C1—H1	0.9500	C5—C6^i	1.3972 (12)
C1—C2	1.3758 (13)	C6—H6	0.9500
C1—C2^i	1.3758 (13)	C6—C7	1.3891 (16)
C2—H2	0.9500	C7—H7	0.9500
C2—C3	1.3931 (15)	C7—C8	1.3829 (13)
C3—H3	0.9500	C8—H8	0.9500
C3—C4	1.3991 (12)
F1—C1—C2	118.88 (7)	C6^i—C5—C4	121.31 (7)
F1—C1—C2^i	118.88 (7)	C6—C5—C4	121.31 (7)
C2^i—C1—H1	118.9	C6—C5—C6^i	117.39 (13)
C2—C1—H1	118.9	C5—C6—H6	119.3
C2—C1—C2^i	122.25 (14)	C7—C6—C5	121.42 (10)
C1—C2—H2	120.7	C7—C6—H6	119.3
C1—C2—C3	118.52 (10)	C6—C7—H7	120.0
C3—C2—H2	120.7	C8—C7—C6	119.97 (10)
C2—C3—H3	119.2	C8—C7—H7	120.0
C2—C3—C4	121.62 (9)	F2—C8—C7^i	120.09 (7)
C4—C3—H3	119.2	F2—C8—C7	120.09 (7)
C3^i—C4—C3	117.48 (13)	C7^i—C8—C7	119.83 (14)
C3^i—C4—C5	121.26 (7)	C7—C8—H8	120.1
C3—C4—C5	121.26 (7)	C7^i—C8—H8	120.1
F1—C1—C2—C3	179.71 (6)	C3^i—C4—C5—C6	179.12 (7)
C1—C2—C3—C4	0.59 (13)	C3—C4—C5—C6	−0.88 (7)
C2^i—C1—C2—C3	−0.29 (6)	C4—C5—C6—C7	179.96 (7)
C2—C3—C4—C3^i	−0.30 (7)	C5—C6—C7—C8	0.07 (14)
C2—C3—C4—C5	179.70 (7)	C6^i—C5—C6—C7	−0.04 (7)
C3^i—C4—C5—C6^i	−0.88 (7)	C6—C7—C8—F2	179.96 (7)
C3—C4—C5—C6^i	179.12 (7)	C6—C7—C8—C7^i	−0.04 (7)

Symmetry code: (i) −x+1, y, −z+1/2.