Fluoro derivatives of bis­(salicyl­idene­aminato-N,O)copper(II) and -oxovan­adium(IV)

The structures of five complexes of fluorine-containing bidentate salicyl­idene­amine Schiff base ligands are reported. These are the bis-ligand copper(II) complexes of the Schiff bases derived from salicyl­aldehyde and 4-fluoro-, [Cu(C₁₃H₉FNO)₂], 3-fluoro-4-methyl-, [Cu(C₁₄H₁₁FNO)₂], 3,5-bis­(tri­fluoro­methyl)-, [Cu(C₁₅H₈F₆NO)₂], and 4-tri­fluoro­methoxy­anilines, [Cu(C₁₄H₉F₃NO₂)₂], and the bis-ligand oxovanadium(IV) complex of the Schiff base derived from salicyl­aldehyde and 4-tri­fluoro­methoxy­aniline, [VO(C₁₄H₉­F₃NO₂)₂]. Three of the copper complexes have square-planar coordination at the metal, imposed by the virtue of symmetry, but the immediate coordination environment of the copper in the 3,5-bis(tri­fluoro­methyl) complex is intermediate between square planar and tetrahedral. The coordination environment at the metal of the vanadium complex can be described as distorted square pyramidal.

S1. Comment

Bidentate Schiff-base ligands of various types and their metal complexes have been extensively studied for many decades. Of the various classes of Schiff base which can be generated by condensation of different types of amines and carbonyl compounds, one of the most popular has been that of the salicylidene-amines, potential O,N-donors derived from (substituted) salicylaldehydes and primary amines. If the amine is aromatic, then a great variety of ligands can be prepared from the great range of substituted anilines which are available. We are interested in the synthesis of fluoro-substituted ligands and metal complexes, in particular in relation to the consequences of fluorine-for-hydrogen replacement on solvation and on reactivity. Here we combine our specific interest in fluoro-derivatized complexes with our general interest in Schiff-base complexes, reporting the preparations and structures of bis-ligand copper(II) complexes of the Schiff bases derived from salicylaldehyde and 4-fluoro-, (I), 3-fluoro-4-methyl-, (II), 3,5-bis-(trifluoromethyl)-, (III), and 4-trifluoromethoxy-anilines, (IV), and the bis-ligand oxovanadium(IV) complex of the Schiff base derived from salicylaldehyde and 4-trifluoromethoxyaniline, (V). \sch

For the copper complexes (I), (II) and (IV), the copper atom and the four ligand donor atoms are coplanar as expected. However, the 3,5-CF₃ substituted complex (III) has a distorted coordination at the Cu atom, intermediate between square-planar and tetrahedral, with an interplanar angle (Cu1—O1—N1 to Cu1—O1'-N1') of 37.8 (1)°. Such distortion may be compared with that engendered by the attachment of relatively bulky groups to the nitrogen donor atoms. This distortion has been of considerable interest to kineticists (Voss et al., 1979). It has been tracked through X-ray diffraction structure determination of e.g. the N-tert-butyl derivative where the angle between the mean planes of the chelate rings is 61.9° (Cheeseman et al., 1966a) and through electronic spectroscopy (Cheeseman et al., 1966b; Voss et al., 1974). For all the Cu complexes the substituted amine ring of each ligand is rotated about the N1—C8 bond from the salicylaldehyde plane. The interplanar angle between these rings are in the range 31.7 (2)° in (II) to 64.3 (1)° in (III). There is no apparent correlation between these angles and the bulk of the respective substituents on the amine-derived moieties of the Schiff-base ligands.

Complexes (II), (III) and (IV) all exhibit disorder at the F atom sites. The F atom of complex (II) was found to be disordered (50:50) between the sites resulting from the possible rotation configurations at the C—N bond. For both complexes (III) and (IV), the F atoms of the CF₃ groups were found to be disordered (50:50) between the two sites staggered by rotation about respectively the C—C or the C—O bond. In both cases, the disordered F atoms have high displacement parameters consistent with further unresolved disorder.

Metal-ligand donor atom bond distances for the copper(II) complexes are summarized in Table 1, which also includes the results of an early structure determination of the parent unsubstituted complex (Baker et al., 1966). Complex (I) has two unique molecules in the triclinic unit cell, for both the molecules the Cu atom is located on a centre of symmetry. The Cu—O bond distances in three of our complexes are the same within experimental uncertainty, but is significantly less in the 3,5-bis(trifluoromethyl) complex. The same can be said of the Cu—N distances. These bond shortenings presumably reflect a small but significant increase in overall bond strength caused by the strongly electron-withdrawing –CF₃ groups. Metal-ligand bond distances in the four substituted complexes appear to be marginally shorter (Cu—O) or marginally longer (Cu—N) than in the unsubstituted complex, though the low precision of the structure of the latter makes comparisons risky.

The Cu—O distances in the salicylideneaniline complexes are similar to those in other O-donor complexes of copper(II). However they are slightly but significantly shorter than those to coordinated oxalate in, for example, the [Cu(ox)₂]^2- anion [Cu—O = 1.933 (5), 1.939 (5) Å; Bloomquist et al., 1981] or in the uncharged ternary complexes [Cu(bipy)(ox)] [Cu—O = 1.984 (4), 1.992 (3) Å; Fitzgerald et al., 1982] or [Cu(N,N-dimethylethane-1,2-diamine-N-oxide)(ox)(H₂O)] [Cu—O_ox = 1.960 (4), 1.965 (5) Å; Pajunen & Nasakkala, 1980], or to the closest water molecules in Cu²⁺_(aq) in various crystal hydrates and in aqueous solution (Cu—O = 1.93 to 2.00 Å; Mani & Rasasershan, 1961; Richens, 1997; Burgess, 1999). Cu—N distances are probably marginally shorter than in various ternary copper ammines containing also coordinated halide or water (Cu—N = 2.03 to 2.05 Å; Colquhoun et al., 1981; Hathaway & Billing, 1970).

The coordination environment at the metal of the vanadium complex (V) could be described as distorted square pyramidal or distorted trigonal bipyramid. In the square pyramidal case, the atoms O1, O1A, N1 and N1A form a plane (maximum deviation 0.186 Å, O1A) with the V atom 0.59 Å above this plane and the terminal O3 atom axial. In the trigonal bipyramid the equatorial plane atoms are V1, O1, O1A and O3 (maximum deviation 0.0235 Å, V1) with N1 and N1A approximately axial (N1—V1—N1A 157.4°). The V—O and V—N distances in the vanadyl complex are V—O_ax = 1.589 (2), V—O_eq = 1.891 (2), 1.904 (2), and V—N = 2.111 (2), 2.121 (3) Å. These V—O distances may be compared with those in the penta- and hexa-hydrates of vanadyl sulfate, V—O_ax = 1.586 (2) and 1.591 (5) Å and V—O_eq = 2.004 (4) to 2.048 (5) Å (Ballhausen et al., 1968; Tachez & Théobald, 1980).

Intra-ligand bond distances for the chelate rings of the copper and oxovanadium complexes of the 4-OCF₃-substituted ligand are compared with their equivalents in the free ligand in Table 2. This shows that the C—O bond contracts significantly on complexation, consistent with a slight increase in double-bond character. However there is no significant shortening of the extra-cyclic C—C bond, as is sometimes observed on chelation (it is already considerably closer to C—C in an aromatic ring than to an aliphatic C—C single bond). On the other hand, the C—N bond joining the aniline-derived nitrogen to its phenyl ring lengthens by a small but significant extent on complexation.

Related literature

For related literature, see: Baker et al. (1966); Ballhausen et al. (1968); Bloomquist et al. (1981); Burgess (1999); Cheeseman et al. (1966a, 1966b); Colquhoun et al. (1981); Fitzgerald et al. (1982); Hathaway & Billing (1970); Pajunen & Nasakkala (1980); Richens (1997); Tachez & Théobald (1980); Voss et al. (1974, 1979).

S2. Experimental

For the copper complexes, a solution of copper acetate (1 mmol) in a 50% ethanol-water mixture (10 cm³) was added to a hot solution of salicylaldehyde (1 mmol) and the appropriate aniline (1 mmol) in ethanol (20 cm³). Precipitation occurred immediately. Reaction mixtures were cooled, filtered and washed with ethanol and recrystallized from CHCl₃. The procedure for the vanadium complex was identical except for starting with vanadyl sulfate (1 mmol).

Computing details

For all compounds, data collection: XSCANS (Fait, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Molecular structure of one of the unique molecules of (I) showing the atom-numbering scheme and 30% displacement ellipsoids. H atoms are drawn as spheres of arbitary radius. [Symmetry code: (i) -x, -y, -z.]
	Fig. 2. Molecular structure of (II) showing the atom-numbering scheme and 30% displacement ellipsoids. Open bonds indicate disordered F atom sites. [Symmetry code: (i) -x, -y, -z.].
	Fig. 3. Molecular structure of (III) showing the atom-numbering scheme and 30% displacement ellipsoids. Open bonds indicate disordered F atom sites. [Symmetry code: (i) -x, y, 1/2 - z].
	Fig. 4. Molecular structure of (IV) showing the atom-numbering scheme and 30% displacement ellipsoids. Open bonds indicate disordered F atom sites. [Symmetry code: (i) -x, 1 - y, -z].
	Fig. 5. Molecular structure of (V) showing the atom-numbering scheme and 30% displacement ellipsoids.

(I)

Crystal data

[Cu(C13H9FNO)2]	Z = 2
Mr = 491.96	F(000) = 502
Triclinic, P1	Dx = 1.542 Mg m^−3
a = 9.995 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.462 (2) Å	Cell parameters from 38 reflections
c = 10.569 (2) Å	θ = 5.3–13.0°
α = 95.13 (2)°	µ = 1.08 mm^−1
β = 92.48 (2)°	T = 190 K
γ = 105.23 (2)°	Block, red
V = 1059.5 (4) Å^3	0.48 × 0.24 × 0.23 mm

Data collection

Bruker P4 diffractometer	2994 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 25.0°, θmin = 2.5°
ω scans	h = −1→11
Absorption correction: analytical (XPREP; SHELXL97)	k = −12→11
Tmin = 0.766, Tmax = 0.810	l = −12→12
4119 measured reflections	3 standard reflections every 100 reflections
3722 independent reflections	intensity decay: <1%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0489P)^2 + 1.4057P] where P = (Fo^2 + 2Fc^2)/3
3722 reflections	(Δ/σ)max = 0.005
301 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Experimental. Two unique molecules were found in the triclinic unit cell. For both molecules the Cu atom is located on a centre of symmetry.

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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.0000	0.0000	0.0000	0.03180 (18)
F1	0.5403 (2)	0.3450 (2)	0.4132 (2)	0.0608 (7)
O1	−0.1121 (3)	−0.1765 (2)	−0.0208 (2)	0.0401 (6)
N1	0.0790 (3)	−0.0260 (3)	0.1708 (3)	0.0322 (6)
C1	−0.1585 (4)	−0.3167 (4)	0.2835 (4)	0.0434 (9)
H1A	−0.1197	−0.3006	0.3669	0.052*
C2	−0.2672 (4)	−0.4260 (4)	0.2502 (4)	0.0501 (10)
H2A	−0.3026	−0.4833	0.3104	0.060*
C3	−0.3246 (4)	−0.4512 (4)	0.1257 (4)	0.0480 (10)
H3A	−0.3988	−0.5258	0.1026	0.058*
C4	−0.2725 (4)	−0.3664 (4)	0.0350 (4)	0.0430 (9)
H4A	−0.3120	−0.3849	−0.0481	0.052*
C5	−0.1606 (4)	−0.2529 (3)	0.0677 (3)	0.0342 (8)
C6	−0.1034 (3)	−0.2277 (3)	0.1951 (3)	0.0324 (7)
C7	0.0166 (4)	−0.1195 (4)	0.2368 (3)	0.0347 (8)
H7A	0.0532	−0.1165	0.3198	0.042*
C8	0.1982 (4)	0.0714 (3)	0.2344 (3)	0.0329 (8)
C9	0.3243 (4)	0.0975 (4)	0.1780 (4)	0.0414 (9)
H9A	0.3308	0.0530	0.0993	0.050*
C10	0.4403 (4)	0.1893 (4)	0.2384 (4)	0.0461 (10)
H10A	0.5253	0.2065	0.2019	0.055*
C11	0.4264 (4)	0.2541 (4)	0.3529 (4)	0.0441 (9)
C12	0.3046 (4)	0.2317 (4)	0.4109 (3)	0.0418 (9)
H12A	0.2992	0.2776	0.4892	0.050*
C13	0.1888 (4)	0.1391 (4)	0.3508 (3)	0.0375 (8)
H13A	0.1046	0.1223	0.3888	0.045*
Cu1A	0.0000	0.5000	0.5000	0.03200 (18)
F1A	0.4334 (3)	0.7889 (3)	0.0701 (2)	0.0647 (7)
O1A	−0.1101 (3)	0.3268 (2)	0.5174 (2)	0.0442 (7)
N1A	0.0465 (3)	0.4422 (3)	0.3255 (3)	0.0317 (6)
C1A	−0.1974 (4)	0.1181 (4)	0.2119 (4)	0.0384 (8)
H1AA	−0.1726	0.1173	0.1281	0.046*
C2A	−0.2975 (4)	0.0130 (4)	0.2464 (4)	0.0437 (9)
H2AA	−0.3411	−0.0582	0.1867	0.052*
C3A	−0.3334 (4)	0.0139 (4)	0.3719 (4)	0.0458 (9)
H3AA	−0.4011	−0.0576	0.3959	0.055*
C4A	−0.2703 (4)	0.1190 (4)	0.4617 (4)	0.0432 (9)
H4AA	−0.2957	0.1167	0.5453	0.052*
C5A	−0.1685 (4)	0.2292 (3)	0.4290 (3)	0.0346 (8)
C6A	−0.1304 (3)	0.2285 (3)	0.3013 (3)	0.0318 (7)
C7A	−0.0223 (3)	0.3314 (3)	0.2597 (3)	0.0326 (8)
H7AA	0.0016	0.3180	0.1765	0.039*
C8A	0.1475 (3)	0.5310 (3)	0.2590 (3)	0.0321 (7)
C9A	0.2861 (4)	0.5714 (4)	0.3047 (4)	0.0412 (9)
H9AA	0.3140	0.5404	0.3784	0.049*
C10A	0.3830 (4)	0.6577 (4)	0.2407 (4)	0.0466 (10)
H10B	0.4762	0.6841	0.2700	0.056*
C11A	0.3388 (4)	0.7032 (4)	0.1336 (4)	0.0439 (9)
C12A	0.2026 (4)	0.6665 (4)	0.0866 (3)	0.0417 (9)
H12B	0.1756	0.6995	0.0137	0.050*
C13A	0.1063 (4)	0.5790 (3)	0.1502 (3)	0.0355 (8)
H13B	0.0135	0.5524	0.1195	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0380 (4)	0.0290 (3)	0.0256 (3)	0.0054 (3)	−0.0018 (2)	0.0007 (2)
F1	0.0491 (14)	0.0592 (15)	0.0560 (15)	−0.0145 (12)	−0.0131 (11)	0.0064 (12)
O1	0.0530 (16)	0.0311 (13)	0.0295 (12)	0.0020 (11)	−0.0038 (11)	−0.0005 (10)
N1	0.0337 (16)	0.0311 (15)	0.0290 (14)	0.0042 (12)	−0.0014 (12)	0.0028 (12)
C1	0.042 (2)	0.047 (2)	0.041 (2)	0.0081 (18)	0.0062 (17)	0.0122 (17)
C2	0.048 (2)	0.046 (2)	0.054 (2)	0.0047 (19)	0.016 (2)	0.0165 (19)
C3	0.040 (2)	0.037 (2)	0.060 (3)	−0.0007 (17)	0.0105 (19)	−0.0012 (18)
C4	0.043 (2)	0.036 (2)	0.045 (2)	0.0047 (17)	−0.0028 (17)	−0.0023 (16)
C5	0.0346 (19)	0.0292 (18)	0.0384 (19)	0.0098 (15)	0.0029 (15)	−0.0020 (15)
C6	0.0331 (18)	0.0311 (18)	0.0336 (18)	0.0087 (15)	0.0038 (14)	0.0047 (14)
C7	0.0337 (19)	0.040 (2)	0.0290 (17)	0.0100 (16)	−0.0023 (14)	0.0011 (15)
C8	0.0320 (18)	0.0357 (19)	0.0301 (17)	0.0079 (15)	−0.0053 (14)	0.0055 (14)
C9	0.039 (2)	0.046 (2)	0.038 (2)	0.0099 (17)	0.0022 (16)	0.0037 (17)
C10	0.033 (2)	0.055 (2)	0.047 (2)	0.0064 (19)	−0.0003 (17)	0.0127 (19)
C11	0.041 (2)	0.042 (2)	0.043 (2)	−0.0002 (17)	−0.0120 (17)	0.0118 (17)
C12	0.048 (2)	0.040 (2)	0.0324 (18)	0.0028 (17)	−0.0008 (16)	0.0044 (16)
C13	0.036 (2)	0.042 (2)	0.0323 (18)	0.0061 (16)	0.0011 (15)	0.0064 (15)
Cu1A	0.0387 (4)	0.0285 (3)	0.0234 (3)	0.0026 (3)	−0.0059 (2)	−0.0027 (2)
F1A	0.0565 (15)	0.0587 (16)	0.0606 (15)	−0.0166 (12)	0.0116 (12)	0.0020 (12)
O1A	0.0601 (17)	0.0340 (14)	0.0280 (13)	−0.0028 (12)	−0.0037 (12)	−0.0038 (11)
N1A	0.0342 (16)	0.0299 (15)	0.0277 (14)	0.0053 (12)	−0.0037 (12)	−0.0025 (12)
C1A	0.037 (2)	0.036 (2)	0.038 (2)	0.0082 (16)	−0.0038 (16)	−0.0085 (15)
C2A	0.042 (2)	0.032 (2)	0.049 (2)	0.0042 (17)	−0.0113 (17)	−0.0127 (17)
C3A	0.043 (2)	0.0301 (19)	0.057 (3)	−0.0003 (16)	−0.0053 (19)	0.0034 (17)
C4A	0.046 (2)	0.040 (2)	0.039 (2)	0.0033 (17)	−0.0027 (17)	0.0066 (16)
C5A	0.039 (2)	0.0281 (18)	0.0339 (18)	0.0063 (15)	−0.0090 (15)	−0.0005 (14)
C6A	0.0312 (18)	0.0279 (17)	0.0335 (18)	0.0066 (14)	−0.0055 (14)	−0.0039 (14)
C7A	0.0316 (18)	0.0364 (19)	0.0274 (17)	0.0088 (15)	−0.0053 (14)	−0.0060 (14)
C8A	0.0323 (18)	0.0291 (17)	0.0301 (17)	0.0032 (14)	−0.0007 (14)	−0.0063 (14)
C9A	0.038 (2)	0.042 (2)	0.038 (2)	0.0052 (17)	−0.0093 (16)	−0.0036 (16)
C10A	0.031 (2)	0.048 (2)	0.051 (2)	−0.0015 (17)	−0.0050 (17)	−0.0093 (18)
C11A	0.045 (2)	0.034 (2)	0.042 (2)	−0.0040 (17)	0.0081 (17)	−0.0039 (16)
C12A	0.051 (2)	0.037 (2)	0.0329 (19)	0.0056 (17)	0.0001 (17)	0.0003 (15)
C13A	0.0357 (19)	0.0350 (19)	0.0296 (17)	0.0032 (15)	−0.0043 (15)	−0.0069 (14)

Geometric parameters (Å, º)

Cu1—O1	1.880 (2)	Cu1A—O1A	1.886 (3)
Cu1—N1	2.009 (3)	Cu1A—N1A	2.002 (3)
F1—C11	1.367 (4)	F1A—C11A	1.366 (4)
O1—C5	1.311 (4)	O1A—C5A	1.314 (4)
N1—C7	1.292 (4)	N1A—C7A	1.302 (4)
N1—C8	1.442 (4)	N1A—C8A	1.435 (4)
C1—C2	1.362 (5)	C1A—C2A	1.367 (5)
C1—C6	1.406 (5)	C1A—C6A	1.421 (5)
C2—C3	1.387 (6)	C2A—C3A	1.388 (6)
C3—C4	1.388 (6)	C3A—C4A	1.380 (5)
C4—C5	1.405 (5)	C4A—C5A	1.403 (5)
C5—C6	1.414 (5)	C5A—C6A	1.419 (5)
C6—C7	1.437 (5)	C6A—C7A	1.426 (5)
C8—C13	1.383 (5)	C8A—C13A	1.385 (5)
C8—C9	1.390 (5)	C8A—C9A	1.389 (5)
C9—C10	1.384 (5)	C9A—C10A	1.384 (5)
C10—C11	1.364 (6)	C10A—C11A	1.366 (6)
C11—C12	1.361 (5)	C11A—C12A	1.371 (5)
C12—C13	1.385 (5)	C12A—C13A	1.385 (5)
O1—Cu1—N1	91.35 (11)	O1A—Cu1A—N1A^ii	88.64 (11)
O1^i—Cu1—N1	88.65 (11)	O1A—Cu1A—N1A	91.36 (11)
C5—O1—Cu1	128.2 (2)	N1A^ii—Cu1A—N1A	180.0
C7—N1—C8	116.2 (3)	C5A—O1A—Cu1A	129.4 (2)
C7—N1—Cu1	122.4 (2)	C7A—N1A—C8A	115.8 (3)
C8—N1—Cu1	120.9 (2)	C7A—N1A—Cu1A	123.1 (2)
C2—C1—C6	121.6 (4)	C8A—N1A—Cu1A	120.5 (2)
C1—C2—C3	119.4 (4)	C2A—C1A—C6A	121.4 (3)
C2—C3—C4	120.8 (4)	C1A—C2A—C3A	119.1 (3)
C3—C4—C5	120.6 (4)	C4A—C3A—C2A	121.2 (4)
O1—C5—C4	119.0 (3)	C3A—C4A—C5A	121.1 (4)
O1—C5—C6	122.8 (3)	O1A—C5A—C4A	119.3 (3)
C4—C5—C6	118.2 (3)	O1A—C5A—C6A	122.6 (3)
C1—C6—C5	119.4 (3)	C4A—C5A—C6A	118.1 (3)
C1—C6—C7	117.8 (3)	C5A—C6A—C1A	119.1 (3)
C5—C6—C7	122.7 (3)	C5A—C6A—C7A	122.6 (3)
N1—C7—C6	126.7 (3)	C1A—C6A—C7A	118.2 (3)
C13—C8—C9	119.6 (3)	N1A—C7A—C6A	127.2 (3)
C13—C8—N1	120.9 (3)	C13A—C8A—C9A	119.6 (3)
C9—C8—N1	119.6 (3)	C13A—C8A—N1A	120.0 (3)
C10—C9—C8	120.4 (4)	C9A—C8A—N1A	120.4 (3)
C11—C10—C9	118.2 (4)	C10A—C9A—C8A	120.2 (4)
C12—C11—C10	123.2 (4)	C11A—C10A—C9A	118.6 (4)
C12—C11—F1	118.2 (4)	F1A—C11A—C10A	119.1 (4)
C10—C11—F1	118.6 (4)	F1A—C11A—C12A	118.2 (4)
C11—C12—C13	118.6 (4)	C10A—C11A—C12A	122.7 (4)
C8—C13—C12	120.1 (3)	C11A—C12A—C13A	118.4 (4)
O1A—Cu1A—O1A^ii	180.0	C8A—C13A—C12A	120.4 (3)

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

(II)

Crystal data

[Cu(C14H11FNO)2]	F(000) = 1068
Mr = 520.02	Dx = 1.486 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 44 reflections
a = 10.752 (1) Å	θ = 4.7–12.4°
b = 7.893 (1) Å	µ = 0.99 mm^−1
c = 27.391 (3) Å	T = 150 K
V = 2324.6 (4) Å^3	Block, red-brown
Z = 4	0.58 × 0.43 × 0.34 mm

Data collection

Bruker P4 diffractometer	1452 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 25.0°, θmin = 3.0°
ω scans	h = −1→12
Absorption correction: analytical (XPREP; SHELXL97)	k = −1→9
Tmin = 0.656, Tmax = 0.777	l = −32→1
2677 measured reflections	3 standard reflections every 100 reflections
2026 independent reflections	intensity decay: <1%

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0598P)^2 + 4.1273P] where P = (Fo^2 + 2Fc^2)/3
2026 reflections	(Δ/σ)max = 0.008
169 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

Special details

Experimental. The F atom was found to be disordered (50:50) between the 3- and 5- sites resulting from the possible rotation configurations of the ring at the C—N bond.

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.0000	0.0000	0.0000	0.0204 (2)
O1	0.0376 (2)	−0.1657 (3)	−0.04724 (8)	0.0269 (6)
N1	−0.0710 (2)	−0.1776 (4)	0.04505 (9)	0.0210 (6)
C1	−0.1806 (3)	−0.5187 (4)	−0.03389 (12)	0.0234 (7)
H1A	−0.2282	−0.5719	−0.0100	0.028*
C2	−0.1807 (3)	−0.5831 (5)	−0.08040 (12)	0.0263 (8)
H2A	−0.2288	−0.6771	−0.0883	0.032*
C3	−0.1069 (3)	−0.5045 (5)	−0.11568 (12)	0.0258 (8)
H3A	−0.1065	−0.5465	−0.1474	0.031*
C4	−0.0347 (3)	−0.3663 (5)	−0.10444 (12)	0.0247 (8)
H4A	0.0143	−0.3172	−0.1286	0.030*
C5	−0.0338 (3)	−0.2973 (4)	−0.05667 (12)	0.0216 (7)
C6	−0.1109 (3)	−0.3751 (4)	−0.02129 (11)	0.0206 (7)
C7	−0.1146 (3)	−0.3194 (4)	0.02853 (11)	0.0209 (7)
H7A	−0.1516	−0.3918	0.0510	0.025*
C8	−0.0860 (3)	−0.1486 (4)	0.09677 (11)	0.0230 (7)
C9	−0.1957 (4)	−0.1862 (5)	0.12066 (12)	0.0305 (8)
H9A	−0.2634	−0.2290	0.1035	0.037*
C10	−0.2033 (4)	−0.1595 (6)	0.17005 (13)	0.0425 (11)
H10	−0.2802	−0.1852	0.1863	0.051*	0.50
F1	−0.3055 (5)	−0.1893 (9)	0.19426 (18)	0.0716 (18)	0.50
C11	−0.1064 (4)	−0.0959 (6)	0.19763 (13)	0.0397 (10)
C12	0.0013 (4)	−0.0587 (6)	0.17221 (14)	0.0371 (10)
H12	0.0713	−0.0153	0.1900	0.044*	0.50
F1'	0.0930 (4)	0.0047 (6)	0.19738 (14)	0.0378 (11)	0.50
C13	0.0135 (3)	−0.0828 (5)	0.12257 (12)	0.0275 (8)
H13A	0.0873	−0.0553	0.1067	0.033*
C14	−0.1177 (5)	−0.0645 (7)	0.25228 (14)	0.0585 (14)
H14D	−0.1989	−0.0979	0.2632	0.088*
H14A	−0.1054	0.0538	0.2589	0.088*
H14B	−0.0558	−0.1295	0.2692	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0207 (3)	0.0248 (3)	0.0158 (3)	−0.0025 (2)	0.0029 (2)	−0.0002 (2)
O1	0.0279 (13)	0.0312 (14)	0.0217 (12)	−0.0054 (11)	0.0055 (11)	−0.0034 (11)
N1	0.0197 (14)	0.0293 (16)	0.0139 (13)	0.0044 (13)	0.0003 (11)	0.0014 (12)
C1	0.0165 (16)	0.0264 (18)	0.0274 (17)	−0.0008 (15)	0.0014 (13)	0.0022 (14)
C2	0.0218 (17)	0.0280 (19)	0.0290 (18)	−0.0004 (16)	−0.0025 (15)	−0.0030 (15)
C3	0.0261 (18)	0.0315 (19)	0.0199 (16)	0.0054 (16)	−0.0033 (14)	−0.0039 (15)
C4	0.0237 (17)	0.0307 (19)	0.0198 (17)	0.0038 (15)	0.0012 (15)	0.0026 (15)
C5	0.0194 (16)	0.0235 (18)	0.0221 (17)	0.0026 (14)	0.0009 (14)	−0.0004 (14)
C6	0.0183 (17)	0.0244 (17)	0.0192 (16)	0.0032 (14)	−0.0007 (13)	0.0024 (14)
C7	0.0184 (17)	0.0246 (18)	0.0197 (16)	0.0012 (14)	0.0010 (13)	0.0058 (14)
C8	0.0259 (17)	0.0259 (18)	0.0172 (16)	0.0017 (15)	0.0017 (14)	0.0025 (14)
C9	0.0289 (19)	0.040 (2)	0.0227 (18)	0.0019 (18)	0.0034 (15)	−0.0014 (16)
C10	0.040 (2)	0.062 (3)	0.025 (2)	0.005 (2)	0.0124 (18)	0.004 (2)
F1	0.059 (3)	0.114 (5)	0.042 (3)	−0.017 (4)	0.019 (3)	−0.007 (3)
C11	0.051 (3)	0.050 (3)	0.0182 (17)	0.007 (2)	0.0030 (18)	−0.0006 (18)
C12	0.043 (2)	0.043 (2)	0.0249 (19)	0.006 (2)	−0.0049 (18)	−0.0037 (17)
F1'	0.034 (2)	0.060 (3)	0.0197 (19)	−0.008 (2)	−0.0132 (18)	−0.013 (2)
C13	0.031 (2)	0.031 (2)	0.0205 (17)	−0.0008 (17)	0.0004 (15)	0.0015 (15)
C14	0.068 (3)	0.087 (4)	0.0207 (19)	0.003 (3)	0.002 (2)	−0.003 (2)

Geometric parameters (Å, º)

Cu1—O1	1.884 (2)	C5—C6	1.415 (5)
Cu1—O1^i	1.884 (2)	C6—C7	1.434 (4)
Cu1—N1	2.017 (3)	C8—C13	1.384 (5)
Cu1—N1^i	2.017 (3)	C8—C9	1.381 (5)
O1—C5	1.317 (4)	C9—C10	1.372 (5)
N1—C7	1.295 (4)	C10—F1	1.305 (6)
N1—C8	1.444 (4)	C10—C11	1.381 (6)
C1—C2	1.372 (5)	C11—C12	1.383 (6)
C1—C6	1.402 (5)	C11—C14	1.522 (5)
C2—C3	1.396 (5)	C12—F1'	1.303 (6)
C3—C4	1.373 (5)	C12—C13	1.379 (5)
C4—C5	1.417 (4)
O1—Cu1—O1^i	180.0 (2)	C1—C6—C7	117.8 (3)
O1—Cu1—N1	91.09 (10)	C5—C6—C7	122.3 (3)
O1^i—Cu1—N1	88.91 (10)	N1—C7—C6	126.0 (3)
O1—Cu1—N1^i	88.91 (10)	C13—C8—C9	119.9 (3)
O1^i—Cu1—N1^i	91.09 (10)	C13—C8—N1	118.3 (3)
N1—Cu1—N1^i	180.00 (11)	C9—C8—N1	121.8 (3)
C5—O1—Cu1	123.8 (2)	C10—C9—C8	119.0 (4)
C7—N1—C8	116.1 (3)	F1—C10—C9	121.6 (5)
C7—N1—Cu1	121.6 (2)	F1—C10—C11	115.0 (4)
C8—N1—Cu1	122.2 (2)	C9—C10—C11	123.4 (4)
C2—C1—C6	121.9 (3)	C10—C11—C12	115.7 (3)
C1—C2—C3	118.6 (3)	C10—C11—C14	122.5 (4)
C4—C3—C2	121.3 (3)	C12—C11—C14	121.8 (4)
C3—C4—C5	121.1 (3)	F1'—C12—C13	120.2 (4)
O1—C5—C6	123.3 (3)	F1'—C12—C11	116.7 (4)
O1—C5—C4	119.2 (3)	C13—C12—C11	123.2 (4)
C6—C5—C4	117.4 (3)	C12—C13—C8	118.8 (4)
C1—C6—C5	119.7 (3)

Symmetry code: (i) −x, −y, −z.

(III)

Crystal data

[Cu(C15H8F6NO)2]	F(000) = 1452
Mr = 727.98	Dx = 1.662 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.607 (2) Å	Cell parameters from 39 reflections
b = 7.423 (1) Å	θ = 5.4–12.6°
c = 27.109 (2) Å	µ = 0.86 mm^−1
β = 98.07 (1)°	T = 290 K
V = 2910.3 (6) Å^3	Block, red-brown
Z = 4	0.47 × 0.36 × 0.33 mm

Data collection

Bruker P4 diffractometer	2013 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 25.0°, θmin = 2.8°
ω scans	h = −1→17
Absorption correction: ψ scan # semi-empirical (using intensity measurements) based on 223 ψ scan data (XEMP; SHELXL97)	k = −1→8
Tmin = 0.761, Tmax = 0.838	l = −32→31
3159 measured reflections	3 standard reflections every 100 reflections
2566 independent reflections	intensity decay: <2%

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0496P)^2 + 1.4869P] where P = (Fo^2 + 2Fc^2)/3
2566 reflections	(Δ/σ)max = 0.003
267 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Experimental. The F atoms of the CF₃ group were found to be disordered (50:50) between two sites staggered by rotation around the C—C bond. The disordered F atoms have high displacement parameters that are consistent with further unresolved disorder about the C—C bond.

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.0000	0.04523 (7)	0.2500	0.04873 (18)
O1	0.07155 (14)	−0.0100 (3)	0.20003 (6)	0.0644 (6)
N1	0.10804 (14)	0.1119 (3)	0.29840 (7)	0.0428 (5)
F1	0.2457 (6)	0.0477 (15)	0.4946 (4)	0.141 (5)	0.68
F2	0.1175 (6)	0.008 (2)	0.5179 (3)	0.166 (5)	0.68
F3	0.1671 (11)	−0.1715 (10)	0.4693 (3)	0.173 (4)	0.68
F1'	0.1640 (14)	0.107 (2)	0.5225 (4)	0.121 (6)	0.32
F2'	0.1169 (11)	−0.133 (3)	0.4888 (7)	0.125 (6)	0.32
F3'	0.2422 (11)	−0.036 (4)	0.4795 (8)	0.134 (9)	0.32
F4	−0.1141 (9)	0.5085 (19)	0.3699 (4)	0.135 (5)	0.60
F5	−0.0082 (6)	0.6369 (12)	0.4171 (8)	0.158 (4)	0.60
F6	−0.0968 (11)	0.462 (2)	0.4450 (5)	0.155 (5)	0.60
F4'	−0.0423 (19)	0.621 (2)	0.3779 (9)	0.162 (8)	0.40
F5'	−0.1383 (8)	0.440 (4)	0.3940 (12)	0.181 (9)	0.40
F6'	−0.0524 (15)	0.548 (3)	0.4493 (4)	0.124 (6)	0.40
C1	0.3113 (2)	0.1352 (4)	0.23410 (13)	0.0676 (9)
H1A	0.3522	0.1719	0.2617	0.081*
C2	0.3413 (3)	0.1227 (5)	0.18828 (16)	0.0841 (12)
H2A	0.4019	0.1522	0.1847	0.101*
C3	0.2805 (3)	0.0657 (6)	0.14766 (15)	0.0870 (12)
H3A	0.3008	0.0573	0.1167	0.104*
C4	0.1915 (3)	0.0216 (5)	0.15185 (11)	0.0775 (11)
H4A	0.1524	−0.0174	0.1238	0.093*
C5	0.1572 (2)	0.0342 (4)	0.19826 (10)	0.0555 (7)
C6	0.21893 (19)	0.0931 (4)	0.23969 (10)	0.0527 (7)
C7	0.19147 (18)	0.1230 (4)	0.28766 (10)	0.0494 (7)
H7A	0.2378	0.1530	0.3135	0.059*
C8	0.09357 (16)	0.1553 (4)	0.34829 (9)	0.0416 (6)
C9	0.13664 (17)	0.0633 (4)	0.38885 (9)	0.0493 (6)
H9A	0.1784	−0.0284	0.3849	0.059*
C10	0.11714 (19)	0.1089 (4)	0.43604 (9)	0.0547 (7)
C11	0.05585 (19)	0.2440 (4)	0.44253 (10)	0.0586 (8)
H11A	0.0435	0.2737	0.4743	0.070*
C12	0.01275 (17)	0.3356 (4)	0.40126 (9)	0.0506 (7)
C13	0.02999 (17)	0.2892 (4)	0.35440 (9)	0.0459 (6)
H13A	−0.0011	0.3478	0.3267	0.055*
C14	0.1618 (3)	0.0015 (7)	0.48027 (13)	0.0826 (12)
C15	−0.0527 (3)	0.4862 (6)	0.40737 (14)	0.0764 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0526 (3)	0.0581 (3)	0.0356 (2)	0.000	0.00683 (18)	0.000
O1	0.0607 (13)	0.0915 (17)	0.0407 (10)	0.0219 (11)	0.0059 (9)	−0.0081 (10)
N1	0.0478 (12)	0.0451 (13)	0.0365 (10)	0.0029 (10)	0.0099 (9)	−0.0012 (9)
F1	0.105 (6)	0.175 (8)	0.120 (6)	−0.001 (5)	−0.061 (5)	0.036 (5)
F2	0.144 (6)	0.285 (15)	0.076 (5)	0.077 (7)	0.044 (5)	0.089 (7)
F3	0.305 (13)	0.092 (4)	0.098 (4)	0.041 (7)	−0.054 (6)	0.033 (4)
F1'	0.179 (16)	0.141 (11)	0.035 (4)	0.055 (9)	−0.013 (7)	0.002 (5)
F2'	0.137 (10)	0.125 (14)	0.111 (12)	−0.040 (10)	0.013 (7)	0.065 (10)
F3'	0.080 (11)	0.22 (2)	0.112 (12)	0.074 (12)	0.039 (10)	0.101 (15)
F4	0.121 (9)	0.183 (12)	0.091 (4)	0.105 (9)	−0.022 (4)	−0.026 (5)
F5	0.129 (5)	0.073 (4)	0.277 (12)	0.010 (3)	0.045 (9)	−0.056 (7)
F6	0.169 (10)	0.174 (11)	0.149 (10)	0.089 (7)	0.113 (9)	0.035 (7)
F4'	0.23 (2)	0.104 (10)	0.179 (12)	0.105 (11)	0.129 (13)	0.060 (10)
F5'	0.053 (4)	0.205 (17)	0.28 (2)	0.034 (7)	0.005 (10)	−0.140 (17)
F6'	0.151 (13)	0.137 (13)	0.078 (7)	0.057 (8)	−0.005 (7)	−0.066 (9)
C1	0.070 (2)	0.0483 (18)	0.092 (2)	0.0023 (15)	0.0360 (18)	−0.0063 (17)
C2	0.089 (3)	0.059 (2)	0.119 (3)	0.009 (2)	0.068 (3)	0.004 (2)
C3	0.113 (3)	0.081 (3)	0.078 (2)	0.037 (2)	0.055 (2)	0.018 (2)
C4	0.097 (3)	0.090 (3)	0.0512 (17)	0.040 (2)	0.0274 (17)	0.0098 (17)
C5	0.069 (2)	0.0529 (17)	0.0472 (15)	0.0237 (16)	0.0178 (13)	0.0061 (14)
C6	0.0620 (17)	0.0404 (16)	0.0610 (17)	0.0073 (13)	0.0275 (14)	−0.0012 (13)
C7	0.0520 (16)	0.0434 (16)	0.0537 (15)	0.0039 (13)	0.0110 (12)	−0.0017 (13)
C8	0.0394 (13)	0.0460 (15)	0.0394 (12)	−0.0006 (12)	0.0055 (10)	−0.0030 (12)
C9	0.0429 (14)	0.0576 (18)	0.0472 (14)	0.0066 (14)	0.0060 (11)	0.0022 (14)
C10	0.0506 (16)	0.071 (2)	0.0414 (14)	0.0005 (15)	0.0024 (12)	0.0063 (13)
C11	0.0571 (17)	0.082 (2)	0.0385 (14)	0.0010 (16)	0.0117 (12)	−0.0066 (14)
C12	0.0455 (15)	0.0581 (18)	0.0487 (15)	0.0047 (13)	0.0090 (12)	−0.0077 (14)
C13	0.0458 (14)	0.0489 (16)	0.0420 (13)	0.0003 (13)	0.0032 (11)	0.0005 (12)
C14	0.083 (3)	0.112 (4)	0.052 (2)	0.013 (3)	0.0061 (19)	0.018 (2)
C15	0.078 (3)	0.087 (3)	0.067 (2)	0.022 (2)	0.020 (2)	−0.008 (2)

Geometric parameters (Å, º)

Cu1—O1^i	1.8688 (18)	F5'—C15	1.297 (13)
Cu1—O1	1.8688 (18)	F6'—C15	1.226 (9)
Cu1—N1	1.969 (2)	C1—C2	1.377 (4)
Cu1—N1^i	1.969 (2)	C1—C6	1.413 (4)
O1—C5	1.300 (4)	C2—C3	1.381 (5)
N1—C7	1.295 (3)	C3—C4	1.360 (5)
N1—C8	1.435 (3)	C4—C5	1.421 (4)
F1—C14	1.279 (9)	C5—C6	1.408 (4)
F2—C14	1.285 (8)	C6—C7	1.431 (3)
F3—C14	1.323 (8)	C8—C9	1.370 (3)
F1'—C14	1.381 (13)	C8—C13	1.386 (3)
F2'—C14	1.234 (13)	C9—C10	1.391 (4)
F3'—C14	1.210 (15)	C10—C11	1.372 (4)
F4—C15	1.268 (8)	C10—C14	1.510 (4)
F5—C15	1.302 (8)	C11—C12	1.383 (4)
F6—C15	1.292 (8)	C12—C13	1.373 (3)
F4'—C15	1.300 (11)	C12—C15	1.496 (4)
O1^i—Cu1—O1	154.66 (15)	F1—C14—F2	108.4 (7)
O1^i—Cu1—N1	92.84 (8)	F3'—C14—F3	71.7 (13)
O1—Cu1—N1	93.48 (8)	F2'—C14—F3	46.2 (8)
O1^i—Cu1—N1^i	93.48 (8)	F1—C14—F3	104.2 (7)
O1—Cu1—N1^i	92.84 (8)	F2—C14—F3	105.5 (7)
N1—Cu1—N1^i	150.87 (13)	F3'—C14—F1'	103.5 (13)
C5—O1—Cu1	127.60 (19)	F2'—C14—F1'	104.6 (10)
C7—N1—C8	117.8 (2)	F1—C14—F1'	71.7 (8)
C7—N1—Cu1	123.90 (18)	F2—C14—F1'	43.7 (6)
C8—N1—Cu1	118.32 (15)	F3—C14—F1'	137.7 (7)
C2—C1—C6	120.8 (3)	F3'—C14—C10	114.9 (7)
C1—C2—C3	119.3 (3)	F2'—C14—C10	113.2 (7)
C4—C3—C2	121.5 (3)	F1—C14—C10	112.9 (6)
C3—C4—C5	121.2 (4)	F2—C14—C10	113.7 (5)
O1—C5—C6	124.1 (2)	F3—C14—C10	111.5 (4)
O1—C5—C4	118.5 (3)	F1'—C14—C10	108.5 (7)
C6—C5—C4	117.4 (3)	F6'—C15—F4	127.2 (7)
C5—C6—C1	119.8 (3)	F6'—C15—F6	41.9 (7)
C5—C6—C7	122.9 (2)	F4—C15—F6	106.0 (7)
C1—C6—C7	117.2 (3)	F6'—C15—F5'	103.5 (9)
N1—C7—C6	126.0 (3)	F4—C15—F5'	42.8 (12)
C9—C8—C13	120.1 (2)	F6—C15—F5'	67.4 (10)
C9—C8—N1	122.2 (2)	F6'—C15—F4'	107.3 (9)
C13—C8—N1	117.6 (2)	F4—C15—F4'	62.5 (11)
C8—C9—C10	119.1 (3)	F6—C15—F4'	134.8 (7)
C11—C10—C9	121.2 (3)	F5'—C15—F4'	102.9 (11)
C11—C10—C14	120.1 (3)	F6'—C15—F5	63.6 (7)
C9—C10—C14	118.7 (3)	F4—C15—F5	109.1 (8)
C10—C11—C12	119.1 (2)	F6—C15—F5	104.4 (7)
C13—C12—C11	120.2 (3)	F5'—C15—F5	135.8 (11)
C13—C12—C15	119.6 (3)	F4'—C15—F5	50.7 (9)
C11—C12—C15	120.2 (3)	F6'—C15—C12	117.6 (7)
C12—C13—C8	120.2 (2)	F4—C15—C12	113.6 (5)
F3'—C14—F2'	111.2 (13)	F6—C15—C12	112.4 (6)
F3'—C14—F1	34.6 (16)	F5'—C15—C12	112.3 (9)
F2'—C14—F1	132.2 (8)	F4'—C15—C12	112.0 (5)
F3'—C14—F2	128.4 (9)	F5—C15—C12	110.8 (4)
F2'—C14—F2	62.5 (8)

Symmetry code: (i) −x, y, −z+1/2.

(IV)

Crystal data

[Cu(C14H9F3NO2)2]	F(000) = 630
Mr = 623.98	Dx = 1.590 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.768 (1) Å	Cell parameters from 38 reflections
b = 10.663 (1) Å	θ = 5.4–13.0°
c = 8.320 (1) Å	µ = 0.92 mm^−1
β = 95.87 (1)°	T = 290 K
V = 1303.3 (2) Å^3	Plate, red
Z = 2	0.59 × 0.49 × 0.18 mm

Data collection

Bruker P4 diffractometer	1877 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 26.5°, θmin = 2.8°
ω scans	h = −18→18
Absorption correction: ψ scan # based on 596 ψ scan data (XEMP; SHELXL97)	k = −13→1
Tmin = 0.678, Tmax = 0.880	l = −1→10
3579 measured reflections	3 standard reflections every 100 reflections
2684 independent reflections	intensity decay: <1%

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0808P)^2 + 0.2587P] where P = (Fo^2 + 2Fc^2)/3
2684 reflections	(Δ/σ)max = 0.034
214 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. The F atoms of the OCF₃ group were refined as disordered (50:50) between two sites involving a rotation about the O—C bond. The disorderd F atoms have high displacement parameters that are consistent with further unresolved disorder about the O—C bond.

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.0000	0.5000	0.0000	0.0504 (2)
O1	−0.09046 (16)	0.4715 (2)	0.1386 (3)	0.0605 (6)
O2	0.45468 (18)	0.6337 (4)	0.1211 (4)	0.1034 (11)
N1	0.08397 (16)	0.5702 (2)	0.1848 (3)	0.0481 (6)
C1	−0.0597 (2)	0.6744 (3)	0.4934 (4)	0.0583 (8)
H1A	−0.0143	0.7188	0.5548	0.070*
C2	−0.1451 (3)	0.6743 (3)	0.5395 (4)	0.0638 (9)
H2A	−0.1582	0.7192	0.6301	0.077*
C3	−0.2129 (2)	0.6063 (3)	0.4498 (4)	0.0627 (9)
H3A	−0.2717	0.6059	0.4806	0.075*
C4	−0.1938 (2)	0.5399 (3)	0.3165 (4)	0.0568 (8)
H4A	−0.2401	0.4946	0.2585	0.068*
C5	−0.1058 (2)	0.5383 (3)	0.2650 (4)	0.0498 (7)
C6	−0.0376 (2)	0.6093 (3)	0.3555 (4)	0.0472 (7)
C7	0.0541 (2)	0.6128 (3)	0.3147 (4)	0.0505 (7)
H7A	0.0968	0.6497	0.3899	0.061*
C8	0.1794 (2)	0.5868 (3)	0.1727 (4)	0.0534 (8)
C9	0.2315 (3)	0.4859 (3)	0.1331 (4)	0.0610 (9)
H9A	0.2042	0.4081	0.1135	0.073*
C10	0.3230 (3)	0.4991 (4)	0.1222 (5)	0.0712 (10)
H10A	0.3583	0.4305	0.0991	0.085*
C11	0.3612 (2)	0.6149 (5)	0.1459 (5)	0.0764 (11)
C12	0.3113 (2)	0.7176 (4)	0.1843 (6)	0.0870 (14)
H12A	0.3389	0.7955	0.2016	0.104*
C13	0.2195 (2)	0.7025 (3)	0.1967 (5)	0.0733 (11)
H13A	0.1845	0.7711	0.2213	0.088*
C14	0.5165 (3)	0.6233 (10)	0.2400 (10)	0.120 (2)
F1	0.5929 (6)	0.6707 (9)	0.1966 (18)	0.142 (3)	0.67
F2	0.4999 (6)	0.6715 (19)	0.3717 (14)	0.171 (8)	0.67
F3	0.5278 (9)	0.5022 (14)	0.2734 (18)	0.186 (5)	0.67
F1'	0.5956 (14)	0.592 (3)	0.217 (4)	0.187 (15)	0.33
F2'	0.5135 (18)	0.743 (3)	0.303 (5)	0.28 (2)	0.33
F3'	0.5016 (19)	0.569 (4)	0.360 (4)	0.222 (19)	0.33

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0541 (3)	0.0448 (3)	0.0503 (3)	−0.0076 (2)	−0.0041 (2)	−0.0045 (3)
O1	0.0639 (14)	0.0628 (15)	0.0542 (14)	−0.0193 (11)	0.0039 (11)	−0.0109 (10)
O2	0.0549 (16)	0.152 (3)	0.103 (2)	−0.0002 (17)	0.0064 (16)	−0.011 (2)
N1	0.0493 (14)	0.0395 (13)	0.0534 (15)	−0.0003 (11)	−0.0052 (11)	0.0010 (12)
C1	0.079 (2)	0.0372 (16)	0.0565 (19)	−0.0013 (15)	−0.0041 (17)	−0.0025 (14)
C2	0.086 (2)	0.0457 (18)	0.061 (2)	0.0084 (18)	0.0150 (18)	−0.0011 (16)
C3	0.066 (2)	0.0512 (19)	0.073 (2)	0.0095 (16)	0.0129 (18)	0.0073 (17)
C4	0.0592 (19)	0.0530 (18)	0.057 (2)	−0.0047 (15)	−0.0007 (15)	0.0052 (15)
C5	0.0587 (18)	0.0407 (15)	0.0477 (18)	−0.0004 (13)	−0.0052 (14)	0.0056 (13)
C6	0.0577 (18)	0.0340 (14)	0.0477 (16)	0.0030 (13)	−0.0058 (13)	0.0040 (13)
C7	0.0568 (18)	0.0376 (15)	0.0530 (17)	−0.0003 (13)	−0.0140 (14)	0.0013 (14)
C8	0.0488 (17)	0.0479 (17)	0.0602 (19)	0.0004 (14)	−0.0096 (14)	0.0039 (15)
C9	0.068 (2)	0.053 (2)	0.061 (2)	0.0051 (16)	−0.0002 (16)	−0.0037 (16)
C10	0.065 (2)	0.080 (3)	0.068 (2)	0.022 (2)	0.0039 (17)	−0.007 (2)
C11	0.0466 (19)	0.105 (3)	0.076 (3)	0.004 (2)	−0.0034 (17)	−0.005 (2)
C12	0.053 (2)	0.068 (2)	0.137 (4)	−0.0102 (19)	−0.006 (2)	−0.012 (3)
C13	0.0541 (19)	0.053 (2)	0.111 (3)	0.0005 (16)	−0.003 (2)	−0.010 (2)
C14	0.055 (3)	0.188 (8)	0.113 (5)	0.013 (4)	−0.002 (3)	−0.036 (6)
F1	0.048 (4)	0.179 (8)	0.199 (7)	0.003 (5)	0.007 (4)	−0.026 (7)
F2	0.085 (5)	0.30 (2)	0.121 (7)	0.019 (10)	−0.009 (5)	−0.107 (11)
F3	0.131 (8)	0.182 (9)	0.232 (13)	0.075 (6)	−0.039 (8)	0.000 (7)
F1'	0.057 (9)	0.31 (4)	0.184 (19)	0.08 (2)	−0.019 (10)	−0.10 (3)
F2'	0.145 (16)	0.29 (3)	0.39 (5)	−0.104 (18)	0.06 (2)	−0.21 (3)
F3'	0.15 (2)	0.32 (5)	0.19 (3)	0.00 (3)	−0.06 (2)	0.11 (3)

Geometric parameters (Å, º)

Cu1—O1	1.877 (2)	C5—C6	1.414 (4)
Cu1—O1^i	1.877 (2)	C6—C7	1.430 (4)
Cu1—N1^i	2.018 (2)	C8—C13	1.374 (5)
Cu1—N1	2.018 (2)	C8—C9	1.382 (5)
O1—C5	1.309 (4)	C9—C10	1.370 (6)
O2—C14	1.280 (7)	C10—C11	1.364 (6)
O2—C11	1.430 (4)	C11—C12	1.376 (6)
N1—C7	1.291 (4)	C12—C13	1.380 (5)
N1—C8	1.434 (4)	C14—F3'	1.19 (3)
C1—C2	1.355 (5)	C14—F1'	1.25 (2)
C1—C6	1.407 (4)	C14—F2	1.257 (12)
C2—C3	1.390 (5)	C14—F1	1.321 (13)
C3—C4	1.370 (5)	C14—F3	1.328 (18)
C4—C5	1.409 (5)	C14—F2'	1.38 (3)
O1—Cu1—O1^i	180.0	C10—C11—C12	122.0 (3)
O1—Cu1—N1^i	89.27 (10)	C10—C11—O2	119.9 (4)
O1^i—Cu1—N1^i	90.73 (10)	C12—C11—O2	118.0 (4)
O1—Cu1—N1	90.73 (10)	C11—C12—C13	118.6 (4)
O1^i—Cu1—N1	89.27 (10)	C8—C13—C12	120.4 (4)
N1^i—Cu1—N1	180.0	F3'—C14—F1'	105 (2)
C5—O1—Cu1	126.7 (2)	F3'—C14—F2	52.9 (19)
C14—O2—C11	119.9 (5)	F1'—C14—F2	120.8 (13)
C7—N1—C8	116.0 (3)	F3'—C14—O2	120.8 (14)
C7—N1—Cu1	122.1 (2)	F1'—C14—O2	120.6 (14)
C8—N1—Cu1	121.6 (2)	F2—C14—O2	116.8 (8)
C2—C1—C6	122.0 (3)	F3'—C14—F1	130.5 (15)
C1—C2—C3	119.3 (3)	F1'—C14—F1	38.7 (16)
C4—C3—C2	120.5 (3)	F2—C14—F1	109.3 (11)
C3—C4—C5	121.7 (3)	O2—C14—F1	108.5 (10)
O1—C5—C4	119.4 (3)	F3'—C14—F3	52 (3)
O1—C5—C6	123.1 (3)	F1'—C14—F3	71.0 (16)
C4—C5—C6	117.4 (3)	F2—C14—F3	104.3 (15)
C1—C6—C5	119.1 (3)	O2—C14—F3	108.1 (9)
C1—C6—C7	119.0 (3)	F1—C14—F3	109.7 (9)
C5—C6—C7	121.8 (3)	F3'—C14—F2'	96 (2)
N1—C7—C6	127.1 (3)	F1'—C14—F2'	111.7 (18)
C13—C8—C9	119.5 (3)	F2—C14—F2'	43.6 (14)
C13—C8—N1	120.8 (3)	O2—C14—F2'	99.5 (17)
C9—C8—N1	119.7 (3)	F1—C14—F2'	79.1 (14)
C10—C9—C8	120.8 (3)	F3—C14—F2'	146 (2)
C11—C10—C9	118.7 (3)

Symmetry code: (i) −x, −y+1, −z.

(V)

Crystal data

[V(C14H9F3NO2)2O]	F(000) = 1268
Mr = 627.38	Dx = 1.574 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.392 (3) Å	Cell parameters from 39 reflections
b = 10.048 (2) Å	θ = 4.8–12.5°
c = 9.654 (1) Å	µ = 0.46 mm^−1
β = 94.84 (1)°	T = 190 K
V = 2647.6 (7) Å^3	Block, orange
Z = 4	0.56 × 0.28 × 0.22 mm

Data collection

Bruker P4 diffractometer	Rint = 0.028
Radiation source: fine-focus sealed tube	θmax = 24.0°, θmin = 2.5°
Graphite monochromator	h = −31→31
ω scans	k = −11→1
5407 measured reflections	l = −1→10
3996 independent reflections	3 standard reflections every 100 reflections
3138 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 1.4703P] where P = (Fo^2 + 2Fc^2)/3
3995 reflections	(Δ/σ)max < 0.001
379 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.34 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.

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

	x	y	z	Uiso*/Ueq
V1	0.242777 (17)	0.37345 (5)	0.35089 (5)	0.02800 (16)
O3	0.23278 (8)	0.4155 (2)	0.1924 (2)	0.0401 (5)
O1	0.19193 (7)	0.42688 (19)	0.4617 (2)	0.0359 (5)
O2	0.48046 (7)	0.5916 (2)	0.3351 (3)	0.0457 (6)
N1	0.28262 (8)	0.5400 (2)	0.4313 (2)	0.0272 (6)
C1	0.20601 (11)	0.7516 (3)	0.6311 (3)	0.0359 (7)
H1A	0.2297	0.8166	0.6511	0.043*
C2	0.16018 (12)	0.7683 (3)	0.6755 (4)	0.0429 (8)
H2A	0.1527	0.8437	0.7256	0.051*
C3	0.12500 (12)	0.6702 (3)	0.6444 (4)	0.0431 (8)
H3B	0.0937	0.6810	0.6733	0.052*
C4	0.13569 (11)	0.5577 (3)	0.5718 (3)	0.0357 (7)
H4A	0.1116	0.4937	0.5524	0.043*
C5	0.18248 (10)	0.5381 (3)	0.5265 (3)	0.0290 (7)
C6	0.21778 (10)	0.6387 (3)	0.5560 (3)	0.0275 (6)
C7	0.26649 (10)	0.6288 (3)	0.5133 (3)	0.0289 (7)
H7A	0.2888	0.6927	0.5481	0.035*
C8	0.33364 (10)	0.5504 (3)	0.4067 (3)	0.0271 (7)
C9	0.34750 (11)	0.5533 (3)	0.2731 (3)	0.0343 (7)
H9A	0.3240	0.5448	0.1982	0.041*
C10	0.39641 (11)	0.5690 (3)	0.2503 (3)	0.0401 (8)
H10A	0.4061	0.5729	0.1603	0.048*
C11	0.43039 (10)	0.5786 (3)	0.3631 (3)	0.0336 (7)
C12	0.41766 (11)	0.5694 (3)	0.4954 (3)	0.0366 (8)
H12A	0.4415	0.5723	0.5698	0.044*
C13	0.36895 (11)	0.5557 (3)	0.5183 (3)	0.0351 (7)
H13A	0.3597	0.5500	0.6086	0.042*
C14	0.50091 (11)	0.7098 (4)	0.3568 (4)	0.0460 (9)
F1	0.50558 (9)	0.7444 (3)	0.4880 (3)	0.0880 (9)
F2	0.47591 (8)	0.8061 (2)	0.2910 (3)	0.0795 (8)
F3	0.54492 (7)	0.7084 (3)	0.3128 (3)	0.0721 (7)
O1A	0.30372 (7)	0.28880 (19)	0.3958 (3)	0.0424 (6)
O2A	0.00732 (7)	0.1315 (2)	0.3282 (2)	0.0452 (6)
N1A	0.21137 (8)	0.1805 (2)	0.3503 (2)	0.0286 (6)
C1A	0.30864 (11)	−0.0715 (3)	0.3644 (3)	0.0318 (7)
H1AA	0.2879	−0.1446	0.3519	0.038*
C2A	0.35828 (11)	−0.0913 (3)	0.3790 (3)	0.0356 (7)
H2AA	0.3712	−0.1769	0.3771	0.043*
C3A	0.38914 (11)	0.0183 (3)	0.3967 (3)	0.0357 (7)
H3AA	0.4229	0.0055	0.4055	0.043*
C4A	0.37078 (11)	0.1444 (3)	0.4012 (3)	0.0376 (8)
H4AA	0.3921	0.2163	0.4131	0.045*
C5A	0.31979 (11)	0.1667 (3)	0.3881 (3)	0.0327 (7)
C6A	0.28835 (10)	0.0566 (3)	0.3680 (3)	0.0284 (7)
C7A	0.23610 (11)	0.0702 (3)	0.3559 (3)	0.0296 (7)
H7AA	0.2180	−0.0082	0.3515	0.036*
C8A	0.15896 (10)	0.1670 (3)	0.3452 (3)	0.0287 (7)
C9A	0.13016 (11)	0.2461 (3)	0.2540 (3)	0.0365 (7)
H9AA	0.1447	0.3072	0.1980	0.044*
C10A	0.07986 (11)	0.2345 (3)	0.2460 (3)	0.0397 (8)
H10B	0.0602	0.2881	0.1857	0.048*
C11A	0.05929 (10)	0.1427 (3)	0.3282 (3)	0.0356 (7)
C12A	0.08689 (11)	0.0632 (3)	0.4204 (3)	0.0380 (8)
H12B	0.0721	0.0019	0.4756	0.046*
C13A	0.13730 (11)	0.0767 (3)	0.4291 (3)	0.0337 (7)
H13B	0.1567	0.0248	0.4916	0.040*
C14A	−0.01696 (12)	0.0865 (4)	0.2138 (4)	0.0491 (9)
F1A	−0.01826 (10)	0.1692 (4)	0.1105 (3)	0.1131 (12)
F2A	0.00147 (8)	−0.0241 (3)	0.1692 (3)	0.1000 (11)
F3A	−0.06253 (6)	0.0622 (2)	0.2406 (2)	0.0602 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0296 (3)	0.0194 (3)	0.0338 (3)	−0.0010 (2)	−0.0039 (2)	−0.0010 (2)
O3	0.0471 (13)	0.0334 (12)	0.0384 (13)	−0.0092 (10)	−0.0054 (10)	0.0008 (10)
O1	0.0326 (11)	0.0249 (11)	0.0503 (14)	−0.0043 (9)	0.0048 (10)	−0.0057 (10)
O2	0.0263 (11)	0.0480 (14)	0.0630 (16)	0.0065 (10)	0.0051 (10)	−0.0079 (12)
N1	0.0278 (12)	0.0208 (12)	0.0324 (14)	−0.0005 (10)	−0.0023 (10)	0.0005 (11)
C1	0.0378 (17)	0.0281 (17)	0.0409 (19)	0.0002 (13)	−0.0012 (14)	−0.0035 (15)
C2	0.047 (2)	0.0326 (18)	0.049 (2)	0.0078 (15)	0.0061 (16)	−0.0082 (16)
C3	0.0363 (17)	0.0389 (19)	0.055 (2)	0.0071 (15)	0.0097 (16)	0.0013 (17)
C4	0.0327 (16)	0.0311 (17)	0.043 (2)	−0.0035 (13)	0.0030 (14)	0.0041 (15)
C5	0.0297 (15)	0.0263 (16)	0.0302 (17)	0.0017 (12)	−0.0031 (12)	0.0032 (13)
C6	0.0326 (15)	0.0229 (15)	0.0261 (16)	−0.0005 (12)	−0.0027 (12)	0.0010 (13)
C7	0.0341 (15)	0.0206 (14)	0.0309 (17)	−0.0035 (13)	−0.0031 (13)	0.0012 (14)
C8	0.0329 (15)	0.0179 (14)	0.0298 (18)	−0.0018 (12)	−0.0011 (13)	−0.0021 (13)
C9	0.0324 (16)	0.0364 (18)	0.0328 (19)	−0.0010 (14)	−0.0056 (13)	−0.0045 (15)
C10	0.0407 (18)	0.048 (2)	0.0330 (19)	0.0002 (16)	0.0078 (14)	−0.0084 (16)
C11	0.0261 (15)	0.0316 (16)	0.043 (2)	0.0070 (13)	0.0004 (14)	−0.0037 (15)
C12	0.0312 (16)	0.0396 (18)	0.037 (2)	0.0011 (14)	−0.0096 (14)	0.0023 (15)
C13	0.0365 (17)	0.0372 (18)	0.0310 (18)	−0.0003 (14)	0.0001 (14)	0.0029 (15)
C14	0.0317 (18)	0.057 (2)	0.050 (2)	0.0021 (17)	0.0078 (16)	0.0073 (19)
F1	0.0890 (18)	0.119 (2)	0.0569 (15)	−0.0580 (17)	0.0132 (13)	−0.0208 (15)
F2	0.0541 (13)	0.0643 (15)	0.121 (2)	0.0095 (12)	0.0106 (13)	0.0380 (15)
F3	0.0348 (11)	0.0877 (17)	0.0963 (18)	−0.0021 (11)	0.0205 (11)	0.0069 (15)
O1A	0.0301 (11)	0.0211 (11)	0.0738 (17)	0.0003 (9)	−0.0093 (11)	−0.0048 (11)
O2A	0.0295 (11)	0.0583 (15)	0.0485 (15)	0.0006 (11)	0.0060 (10)	−0.0112 (13)
N1A	0.0310 (13)	0.0239 (13)	0.0298 (14)	−0.0029 (11)	−0.0040 (10)	0.0002 (11)
C1A	0.0414 (17)	0.0246 (15)	0.0291 (17)	−0.0001 (13)	0.0008 (13)	0.0024 (13)
C2A	0.0490 (19)	0.0250 (16)	0.0324 (18)	0.0093 (14)	0.0017 (14)	0.0024 (14)
C3A	0.0376 (17)	0.0336 (17)	0.0352 (18)	0.0077 (14)	−0.0013 (14)	0.0033 (15)
C4A	0.0323 (16)	0.0319 (17)	0.047 (2)	−0.0006 (14)	−0.0050 (14)	0.0005 (15)
C5A	0.0379 (17)	0.0220 (16)	0.0369 (18)	0.0010 (13)	−0.0047 (14)	−0.0010 (14)
C6A	0.0330 (15)	0.0230 (15)	0.0285 (17)	0.0014 (13)	−0.0015 (12)	−0.0001 (13)
C7A	0.0403 (17)	0.0223 (15)	0.0255 (17)	−0.0051 (14)	−0.0010 (13)	−0.0011 (13)
C8A	0.0307 (15)	0.0234 (15)	0.0309 (17)	−0.0023 (12)	−0.0038 (13)	−0.0066 (13)
C9A	0.0346 (17)	0.0296 (17)	0.0443 (19)	−0.0050 (13)	−0.0025 (14)	0.0040 (15)
C10A	0.0349 (17)	0.0341 (17)	0.048 (2)	0.0022 (14)	−0.0067 (15)	0.0025 (16)
C11A	0.0299 (15)	0.0391 (18)	0.0378 (19)	−0.0022 (14)	0.0029 (14)	−0.0078 (16)
C12A	0.0413 (18)	0.0390 (18)	0.0344 (19)	−0.0047 (15)	0.0060 (14)	0.0021 (15)
C13A	0.0396 (17)	0.0328 (16)	0.0280 (17)	0.0003 (14)	−0.0015 (13)	−0.0013 (14)
C14A	0.0356 (19)	0.054 (2)	0.058 (3)	−0.0079 (17)	0.0070 (17)	−0.003 (2)
F1A	0.0808 (19)	0.167 (3)	0.085 (2)	−0.061 (2)	−0.0303 (15)	0.049 (2)
F2A	0.0482 (13)	0.108 (2)	0.145 (3)	−0.0075 (14)	0.0133 (15)	−0.082 (2)
F3A	0.0298 (10)	0.0668 (14)	0.0841 (16)	−0.0058 (10)	0.0048 (10)	−0.0090 (12)

Geometric parameters (Å, º)

V1—O3	1.589 (2)	C14—F3	1.312 (4)
V1—O1A	1.891 (2)	C14—F2	1.317 (4)
V1—O1	1.904 (2)	O1A—C5A	1.308 (3)
V1—N1	2.110 (2)	O2A—C14A	1.320 (4)
V1—N1A	2.121 (2)	O2A—C11A	1.428 (3)
O1—C5	1.317 (3)	N1A—C7A	1.297 (4)
O2—C14	1.322 (4)	N1A—C8A	1.439 (4)
O2—C11	1.426 (3)	C1A—C2A	1.370 (4)
N1—C7	1.295 (4)	C1A—C6A	1.404 (4)
N1—C8	1.441 (3)	C2A—C3A	1.390 (4)
C1—C2	1.371 (4)	C3A—C4A	1.366 (4)
C1—C6	1.399 (4)	C4A—C5A	1.409 (4)
C2—C3	1.394 (5)	C5A—C6A	1.405 (4)
C3—C4	1.374 (5)	C6A—C7A	1.433 (4)
C4—C5	1.403 (4)	C8A—C13A	1.383 (4)
C5—C6	1.411 (4)	C8A—C9A	1.383 (4)
C6—C7	1.433 (4)	C9A—C10A	1.378 (4)
C8—C9	1.374 (4)	C10A—C11A	1.368 (4)
C8—C13	1.387 (4)	C11A—C12A	1.374 (4)
C9—C10	1.385 (4)	C12A—C13A	1.383 (4)
C10—C11	1.375 (4)	C14A—F1A	1.297 (5)
C11—C12	1.355 (4)	C14A—F2A	1.308 (4)
C12—C13	1.378 (4)	C14A—F3A	1.319 (4)
C14—F1	1.310 (4)
O3—V1—O1A	114.69 (11)	F1—C14—F2	106.0 (3)
O3—V1—O1	113.04 (11)	F3—C14—F2	107.8 (3)
O1A—V1—O1	132.17 (10)	F1—C14—O2	113.4 (3)
O3—V1—N1	100.66 (10)	F3—C14—O2	109.1 (3)
O1A—V1—N1	81.55 (9)	F2—C14—O2	112.8 (3)
O1—V1—N1	87.12 (9)	C5A—O1A—V1	134.73 (19)
O3—V1—N1A	101.76 (10)	C14A—O2A—C11A	117.3 (3)
O1A—V1—N1A	86.53 (9)	C7A—N1A—C8A	115.9 (2)
O1—V1—N1A	86.77 (9)	C7A—N1A—V1	124.78 (19)
N1—V1—N1A	157.40 (9)	C8A—N1A—V1	119.29 (18)
C5—O1—V1	133.51 (18)	C2A—C1A—C6A	121.5 (3)
C14—O2—C11	117.0 (2)	C1A—C2A—C3A	119.1 (3)
C7—N1—C8	115.9 (2)	C4A—C3A—C2A	121.2 (3)
C7—N1—V1	125.36 (19)	C3A—C4A—C5A	120.6 (3)
C8—N1—V1	118.39 (17)	O1A—C5A—C6A	122.7 (3)
C2—C1—C6	121.2 (3)	O1A—C5A—C4A	118.7 (3)
C1—C2—C3	118.7 (3)	C6A—C5A—C4A	118.6 (3)
C4—C3—C2	121.2 (3)	C1A—C6A—C5A	119.1 (3)
C3—C4—C5	120.9 (3)	C1A—C6A—C7A	118.7 (3)
O1—C5—C4	119.2 (3)	C5A—C6A—C7A	122.2 (3)
O1—C5—C6	123.0 (3)	N1A—C7A—C6A	126.8 (3)
C4—C5—C6	117.7 (3)	C13A—C8A—C9A	120.0 (3)
C1—C6—C5	120.1 (3)	C13A—C8A—N1A	121.2 (3)
C1—C6—C7	117.8 (3)	C9A—C8A—N1A	118.8 (3)
C5—C6—C7	122.1 (3)	C10A—C9A—C8A	120.1 (3)
N1—C7—C6	126.7 (3)	C11A—C10A—C9A	118.9 (3)
C9—C8—C13	119.9 (3)	C10A—C11A—C12A	122.4 (3)
C9—C8—N1	120.3 (3)	C10A—C11A—O2A	120.8 (3)
C13—C8—N1	119.8 (3)	C12A—C11A—O2A	116.6 (3)
C8—C9—C10	119.9 (3)	C11A—C12A—C13A	118.3 (3)
C11—C10—C9	118.8 (3)	C8A—C13A—C12A	120.3 (3)
C12—C11—C10	122.1 (3)	F1A—C14A—F2A	106.1 (4)
C12—C11—O2	120.8 (3)	F1A—C14A—F3A	107.7 (3)
C10—C11—O2	117.0 (3)	F2A—C14A—F3A	107.8 (3)
C11—C12—C13	119.2 (3)	F1A—C14A—O2A	113.8 (3)
C12—C13—C8	120.0 (3)	F2A—C14A—O2A	112.6 (3)
F1—C14—F3	107.4 (3)	F3A—C14A—O2A	108.6 (3)