Mono- and dinuclear Cu^II complexes of the benzyl­dipicolyl­amine (BDPA) ligand: crystal structure, synthesis and characterization

The crystal structures of mono- and dinuclear Cu^II tri­fluoro­methane­sulfonate (triflate) complexes with benzyl­dipicolyl­amine (BDPA) are described. From equimolar amounts of Cu(triflate)₂ and BDPA, a water-bound Cu^II mononuclear complex, aqua(benzyldipicolylamine-κ³N,N′,N′′)bis(trifluoromethanesulfonato-κO)copper(II) tetrahydrofuran monosolvate, [Cu(CF₃SO₃)₂(C₁₉H₁₉N₃)(H₂O)]·C₄H₈O, (I), and a triflate-bridged Cu^II dinuclear complex, bis(μ-trifluoro­me­thanesulfonato-κ²O:O′)bis[(benzyldipicolylamine-κ³N,N′,N′′)(trifluoromethane­sulfonato-κO)copper(II)], [Cu₂(CF₃SO₃)₄(C₁₉H₁₉N₃)₂], were synthesized. The presence of residual moisture in the reaction medium afforded water-bound complex (I), whereas dinuclear complex (II) was synthesized from an anhydrous reaction medium. Single-crystal X-ray structure analysis reveals that the Cu^II centres adopt slightly distorted octa­hedral geometries in both complexes. The metal-bound water mol­ecule in (I) is involved in inter­molecular O—H...O hydrogen bonds with triflate ligands and tetrahydrofuran solvent molecules. In (II), weak inter­molecular C—H...F(triflate) and C—H...O(triflate) hydrogen bonds stabilize the crystal lattice. Complexes (I) and (II) were also characterized fully using FT–IR and UV–Vis spectroscopy, cyclic voltammetry and elemental analysis.

Computing details

For both structures, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SHELXS-97 (Sheldrick, 2008) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (I); SHELXL-97 (Sheldrick, 2008) for (II). For both structures, molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Aqua(benzyldipicolylamine-κ³N,N',N'')bis(trifluoromethanesulfonato-κO)copper(II) tetrahydrofuran monosolvate (I)

Crystal data

[Cu(CF3O3S)2(C19H19N3)(H2O)]·C4H8O	Z = 2
Mr = 741.17	F(000) = 758
Triclinic, P1	Dx = 1.613 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8133 (19) Å	Cell parameters from 1904 reflections
b = 11.800 (3) Å	θ = 2.6–21.9°
c = 15.404 (3) Å	µ = 0.94 mm^−1
α = 96.363 (5)°	T = 200 K
β = 93.886 (5)°	Block, blue
γ = 105.518 (5)°	0.23 × 0.11 × 0.11 mm
V = 1526.1 (6) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	5373 independent reflections
Radiation source: fine-focus sealed tube	2353 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.802, Tmax = 0.903	k = −12→14
8947 measured reflections	l = −16→18

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 0.73	w = 1/[σ^2(Fo^2) + (0.0173P)^2] where P = (Fo^2 + 2Fc^2)/3
5373 reflections	(Δ/σ)max < 0.001
411 parameters	Δρmax = 0.48 e Å^−3
2 restraints	Δρmin = −0.37 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.

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 > 2sigma(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
C25	−0.0731 (11)	0.4114 (10)	0.6205 (7)	0.145 (4)
H25A	−0.1601	0.3702	0.5744	0.175*
H25B	−0.0839	0.4910	0.6414	0.175*
Cu1	0.74646 (8)	0.97585 (6)	0.72992 (4)	0.0382 (2)
O1	0.7993 (5)	1.1045 (4)	0.6564 (3)	0.0504 (12)
H1	0.7157	1.1123	0.6315	0.076*
N1	0.9217 (5)	0.9089 (4)	0.6989 (3)	0.0375 (12)
C1	1.0085 (7)	0.9304 (5)	0.6300 (4)	0.0488 (17)
H1A	0.9886	0.9847	0.5926	0.059*
C2	1.1248 (7)	0.8751 (6)	0.6130 (4)	0.0551 (18)
H2	1.1871	0.8934	0.5658	0.066*
C3	1.1493 (7)	0.7943 (6)	0.6645 (4)	0.0613 (19)
H3	1.2264	0.7533	0.6522	0.074*
C4	1.0608 (7)	0.7716 (5)	0.7356 (4)	0.0494 (17)
H4	1.0773	0.7159	0.7728	0.059*
C5	0.9494 (6)	0.8317 (5)	0.7505 (3)	0.0358 (14)
C6	0.8532 (6)	0.8209 (5)	0.8288 (3)	0.0371 (15)
H6A	0.8367	0.7406	0.8463	0.044*
H6B	0.9114	0.8796	0.8791	0.044*
N2	0.7002 (5)	0.8418 (4)	0.8061 (3)	0.0342 (12)
C7	0.5855 (6)	0.7349 (4)	0.7534 (3)	0.0377 (15)
H7A	0.6320	0.7152	0.6990	0.045*
H7B	0.4879	0.7567	0.7359	0.045*
C8	0.5391 (7)	0.6247 (5)	0.7976 (3)	0.0385 (15)
C9	0.6154 (7)	0.5390 (5)	0.7835 (4)	0.0503 (17)
H9	0.6985	0.5508	0.7464	0.060*
C10	0.5752 (8)	0.4336 (6)	0.8220 (4)	0.067 (2)
H10	0.6275	0.3738	0.8100	0.081*
C11	0.4564 (9)	0.4199 (6)	0.8780 (4)	0.067 (2)
H11	0.4293	0.3513	0.9070	0.081*
C12	0.3796 (8)	0.5038 (6)	0.8913 (4)	0.068 (2)
H12	0.2966	0.4928	0.9285	0.082*
C13	0.4192 (7)	0.6052 (5)	0.8518 (4)	0.0542 (18)
H13	0.3629	0.6630	0.8620	0.065*
N3	0.5624 (5)	1.0108 (4)	0.7802 (3)	0.0353 (12)
C14	0.4726 (7)	1.0774 (5)	0.7520 (4)	0.0477 (17)
H14	0.4999	1.1157	0.7019	0.057*
C15	0.3421 (7)	1.0934 (5)	0.7919 (4)	0.0529 (17)
H15	0.2825	1.1423	0.7702	0.064*
C16	0.3016 (7)	1.0367 (6)	0.8632 (4)	0.0559 (18)
H16	0.2133	1.0463	0.8923	0.067*
C17	0.3892 (6)	0.9664 (5)	0.8922 (4)	0.0447 (16)
H17	0.3593	0.9246	0.9404	0.054*
C18	0.5204 (6)	0.9555 (5)	0.8521 (3)	0.0356 (14)
C19	0.6315 (6)	0.8884 (5)	0.8817 (3)	0.0358 (14)
H19A	0.7171	0.9415	0.9243	0.043*
H19B	0.5740	0.8220	0.9114	0.043*
S1	0.54892 (19)	0.83768 (13)	0.50701 (10)	0.0446 (4)
O2	0.5680 (4)	0.8758 (3)	0.5990 (2)	0.0501 (11)
O3	0.4030 (5)	0.8420 (3)	0.4633 (2)	0.0593 (12)
O4	0.6865 (5)	0.8798 (4)	0.4615 (3)	0.0796 (15)
C20	0.5276 (9)	0.6802 (6)	0.5003 (4)	0.0585 (19)
F1	0.4985 (5)	0.6269 (3)	0.4182 (2)	0.0921 (14)
F2	0.4067 (5)	0.6287 (3)	0.5444 (2)	0.0841 (13)
F3	0.6566 (5)	0.6577 (3)	0.5359 (2)	0.0817 (12)
S2	0.97200 (18)	0.17906 (14)	0.93689 (10)	0.0423 (4)
O5	0.9239 (4)	0.1301 (3)	0.8473 (2)	0.0624 (13)
O6	1.1367 (4)	0.2387 (3)	0.9567 (2)	0.0581 (12)
O7	0.9050 (4)	0.1005 (3)	0.9978 (2)	0.0504 (11)
C21	0.8772 (8)	0.2939 (6)	0.9548 (5)	0.064 (2)
F4	0.9208 (5)	0.3800 (3)	0.9082 (3)	0.1041 (16)
F5	0.7203 (4)	0.2514 (3)	0.9410 (3)	0.0886 (13)
F6	0.9056 (5)	0.3439 (4)	1.0397 (3)	0.0978 (14)
O8	−0.0659 (10)	0.3398 (7)	0.6943 (4)	0.182 (4)
C24	0.0696 (14)	0.4174 (11)	0.5927 (7)	0.170 (5)
H24A	0.1250	0.5000	0.5851	0.204*
H24B	0.0586	0.3662	0.5358	0.204*
C22	0.0792 (15)	0.3717 (12)	0.7265 (7)	0.186 (6)
H22A	0.1056	0.4499	0.7635	0.223*
H22B	0.1033	0.3125	0.7620	0.223*
C23	0.1538 (14)	0.3773 (15)	0.6581 (7)	0.263 (10)
H23A	0.1646	0.2979	0.6365	0.315*
H23B	0.2612	0.4326	0.6727	0.315*
H1B	0.849 (6)	1.176 (2)	0.669 (3)	0.05 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C25	0.093 (8)	0.251 (14)	0.125 (9)	0.084 (8)	0.010 (7)	0.069 (9)
Cu1	0.0419 (4)	0.0443 (5)	0.0287 (4)	0.0082 (3)	0.0091 (3)	0.0118 (3)
O1	0.054 (3)	0.047 (3)	0.046 (3)	0.000 (3)	0.001 (2)	0.022 (2)
N1	0.037 (3)	0.046 (3)	0.025 (3)	0.001 (2)	0.008 (2)	0.006 (2)
C1	0.049 (4)	0.059 (5)	0.038 (4)	0.011 (3)	0.012 (3)	0.012 (3)
C2	0.048 (4)	0.067 (5)	0.051 (4)	0.014 (4)	0.023 (4)	0.006 (4)
C3	0.046 (4)	0.077 (6)	0.062 (5)	0.024 (4)	0.013 (4)	−0.007 (4)
C4	0.043 (4)	0.057 (5)	0.049 (4)	0.014 (3)	0.003 (3)	0.011 (3)
C5	0.026 (3)	0.045 (4)	0.031 (3)	0.003 (3)	0.001 (3)	0.005 (3)
C6	0.031 (3)	0.043 (4)	0.035 (4)	0.007 (3)	−0.005 (3)	0.009 (3)
N2	0.040 (3)	0.039 (3)	0.021 (3)	0.006 (2)	0.004 (2)	0.003 (2)
C7	0.040 (3)	0.038 (4)	0.034 (3)	0.007 (3)	0.003 (3)	0.006 (3)
C8	0.040 (4)	0.038 (4)	0.033 (3)	0.005 (3)	0.001 (3)	0.001 (3)
C9	0.051 (4)	0.048 (5)	0.050 (4)	0.010 (3)	0.012 (3)	0.007 (3)
C10	0.089 (5)	0.046 (5)	0.070 (5)	0.022 (4)	0.004 (4)	0.018 (4)
C11	0.092 (6)	0.044 (5)	0.063 (5)	0.007 (4)	0.004 (4)	0.026 (4)
C12	0.082 (5)	0.055 (5)	0.062 (5)	0.001 (4)	0.033 (4)	0.011 (4)
C13	0.059 (4)	0.044 (4)	0.060 (4)	0.011 (3)	0.024 (4)	0.008 (3)
N3	0.048 (3)	0.030 (3)	0.027 (3)	0.008 (2)	0.001 (2)	0.007 (2)
C14	0.052 (4)	0.046 (4)	0.042 (4)	0.008 (3)	0.002 (3)	0.006 (3)
C15	0.047 (4)	0.046 (4)	0.070 (5)	0.023 (3)	0.006 (4)	−0.001 (4)
C16	0.047 (4)	0.064 (5)	0.058 (5)	0.015 (4)	0.020 (4)	0.002 (4)
C17	0.038 (4)	0.056 (5)	0.039 (4)	0.010 (3)	0.018 (3)	0.002 (3)
C18	0.039 (4)	0.031 (4)	0.029 (3)	0.000 (3)	−0.001 (3)	−0.002 (3)
C19	0.043 (4)	0.043 (4)	0.023 (3)	0.011 (3)	0.009 (3)	0.006 (3)
S1	0.0575 (11)	0.0448 (11)	0.0328 (9)	0.0145 (8)	0.0041 (8)	0.0094 (8)
O2	0.078 (3)	0.047 (3)	0.028 (2)	0.021 (2)	−0.001 (2)	0.0071 (19)
O3	0.070 (3)	0.063 (3)	0.046 (3)	0.022 (2)	−0.010 (2)	0.013 (2)
O4	0.078 (3)	0.090 (4)	0.071 (3)	0.008 (3)	0.041 (3)	0.034 (3)
C20	0.080 (5)	0.063 (5)	0.035 (4)	0.023 (4)	0.012 (4)	0.007 (4)
F1	0.152 (4)	0.073 (3)	0.051 (3)	0.041 (3)	0.008 (3)	−0.017 (2)
F2	0.102 (3)	0.057 (3)	0.082 (3)	−0.003 (2)	0.017 (3)	0.016 (2)
F3	0.107 (3)	0.082 (3)	0.077 (3)	0.059 (3)	0.008 (2)	0.017 (2)
S2	0.0443 (10)	0.0431 (10)	0.0366 (10)	0.0078 (8)	0.0055 (8)	0.0037 (8)
O5	0.068 (3)	0.073 (3)	0.028 (2)	−0.009 (2)	0.001 (2)	−0.003 (2)
O6	0.037 (2)	0.067 (3)	0.059 (3)	−0.003 (2)	0.007 (2)	0.000 (2)
O7	0.054 (3)	0.045 (3)	0.047 (3)	0.001 (2)	0.003 (2)	0.015 (2)
C21	0.049 (5)	0.066 (6)	0.078 (6)	0.014 (4)	0.008 (4)	0.023 (5)
F4	0.125 (4)	0.064 (3)	0.133 (4)	0.025 (3)	0.023 (3)	0.054 (3)
F5	0.061 (3)	0.087 (3)	0.129 (4)	0.035 (2)	0.008 (3)	0.028 (3)
F6	0.125 (4)	0.079 (3)	0.093 (4)	0.041 (3)	0.024 (3)	−0.012 (3)
O8	0.175 (7)	0.204 (8)	0.077 (5)	−0.101 (6)	−0.032 (5)	0.050 (5)
C24	0.148 (10)	0.291 (15)	0.115 (9)	0.086 (10)	0.044 (8)	0.128 (10)
C22	0.152 (11)	0.251 (15)	0.112 (10)	−0.017 (11)	−0.053 (9)	0.071 (10)
C23	0.211 (14)	0.61 (3)	0.094 (9)	0.266 (17)	0.114 (9)	0.166 (14)

Geometric parameters (Å, º)

Cu1—O1	1.969 (3)	N3—C18	1.369 (6)
Cu1—N1	1.977 (5)	C14—C15	1.387 (7)
Cu1—N2	2.043 (4)	C15—C16	1.367 (7)
Cu1—N3	1.964 (5)	C16—C17	1.365 (7)
C25—C24	1.342 (10)	C17—C18	1.376 (7)
C25—O8	1.498 (9)	C18—C19	1.493 (7)
N1—C5	1.332 (6)	S1—O2	1.423 (4)
N1—C1	1.357 (6)	S1—O3	1.427 (4)
C1—C2	1.379 (8)	S1—O4	1.442 (4)
C2—C3	1.356 (8)	S1—C20	1.807 (7)
C3—C4	1.396 (7)	C20—F1	1.325 (7)
C4—C5	1.374 (7)	C20—F3	1.331 (7)
C5—C6	1.518 (7)	C20—F2	1.345 (6)
C6—N2	1.461 (6)	S2—O5	1.426 (4)
N2—C19	1.468 (6)	S2—O6	1.428 (4)
N2—C7	1.501 (6)	S2—O7	1.436 (3)
C7—C8	1.507 (6)	S2—C21	1.780 (7)
C8—C9	1.363 (8)	C21—F4	1.298 (6)
C8—C13	1.377 (7)	C21—F5	1.332 (6)
C9—C10	1.407 (7)	C21—F6	1.352 (7)
C10—C11	1.390 (8)	O8—C22	1.279 (10)
C11—C12	1.346 (9)	C24—C23	1.408 (12)
C12—C13	1.375 (7)	C22—C23	1.278 (12)
N3—C14	1.339 (7)
N3—Cu1—O1	99.34 (19)	N3—C14—C15	123.6 (5)
N3—Cu1—N1	165.45 (17)	C16—C15—C14	118.2 (6)
O1—Cu1—N1	95.19 (18)	C17—C16—C15	119.4 (6)
N3—Cu1—N2	82.69 (17)	C16—C17—C18	120.5 (5)
O1—Cu1—N2	177.83 (19)	N3—C18—C17	121.0 (5)
N1—Cu1—N2	82.77 (17)	N3—C18—C19	113.6 (5)
C5—N1—Cu1	114.5 (4)	C17—C18—C19	125.3 (5)
C1—N1—Cu1	126.7 (4)	N2—C19—C18	110.1 (4)
C24—C25—O8	99.4 (8)	O2—S1—O3	114.4 (3)
C5—N1—C1	118.8 (5)	O2—S1—O4	115.6 (3)
N1—C1—C2	121.5 (6)	O3—S1—O4	115.1 (2)
C3—C2—C1	119.3 (6)	O2—S1—C20	103.3 (3)
C2—C3—C4	119.7 (6)	O3—S1—C20	102.9 (3)
C5—C4—C3	118.4 (6)	O4—S1—C20	103.1 (3)
N1—C5—C4	122.3 (5)	F1—C20—F3	107.8 (6)
N1—C5—C6	114.2 (5)	F1—C20—F2	107.7 (6)
C4—C5—C6	123.5 (5)	F3—C20—F2	107.0 (5)
N2—C6—C5	109.9 (4)	F1—C20—S1	112.2 (4)
C6—N2—C19	113.8 (4)	F3—C20—S1	112.0 (5)
C6—N2—C7	112.0 (4)	F2—C20—S1	110.0 (5)
C19—N2—C7	111.9 (4)	O5—S2—O6	115.2 (2)
C6—N2—Cu1	105.3 (3)	O5—S2—O7	113.5 (2)
C19—N2—Cu1	104.7 (3)	O6—S2—O7	115.2 (2)
C7—N2—Cu1	108.4 (3)	O5—S2—C21	104.4 (3)
N2—C7—C8	116.7 (4)	O6—S2—C21	104.1 (3)
C9—C8—C13	117.7 (5)	O7—S2—C21	102.3 (3)
C9—C8—C7	119.9 (5)	F4—C21—F5	108.2 (6)
C13—C8—C7	122.5 (6)	F4—C21—F6	106.4 (6)
C8—C9—C10	122.2 (6)	F5—C21—F6	104.6 (6)
C11—C10—C9	117.8 (6)	F4—C21—S2	115.0 (5)
C12—C11—C10	120.0 (6)	F5—C21—S2	111.5 (5)
C11—C12—C13	121.0 (6)	F6—C21—S2	110.6 (5)
C12—C13—C8	121.2 (6)	C22—O8—C25	105.3 (7)
C14—N3—C18	117.2 (5)	C25—C24—C23	105.9 (8)
C14—N3—Cu1	128.7 (4)	C23—C22—O8	102.9 (10)
C18—N3—Cu1	114.0 (4)	C22—C23—C24	109.1 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.84	1.94	2.719 (5)	153
O1—H1B···O8^ii	0.84 (2)	1.86 (2)	2.691 (8)	172 (6)

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

Bis(µ-trifluoromethanesulfonato-κ²O:O')bis[(benzyldipicolylamine-κ³N,N',N'')(trifluoromethanesulfonato-κO)copper(II)] (II)

Crystal data

[Cu2(CF3O3S)4(C19H19N3)2]	Z = 1
Mr = 1302.12	F(000) = 658
Triclinic, P1	Dx = 1.731 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8793 (5) Å	Cell parameters from 3859 reflections
b = 10.5542 (6) Å	θ = 2.7–28.2°
c = 14.1620 (8) Å	µ = 1.13 mm^−1
α = 103.357 (1)°	T = 273 K
β = 94.115 (1)°	Block, blue
γ = 102.742 (1)°	0.33 × 0.22 × 0.16 mm
V = 1248.90 (12) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	6086 independent reflections
Radiation source: fine-focus sealed tube	4109 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 28.3°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
Tmin = 0.707, Tmax = 0.840	k = −13→10
9293 measured reflections	l = −18→18

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.259	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0728P)^2 + 10.1901P] where P = (Fo^2 + 2Fc^2)/3
6086 reflections	(Δ/σ)max < 0.001
352 parameters	Δρmax = 1.52 e Å^−3
0 restraints	Δρmin = −2.48 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.

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 > 2sigma(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	0.53776 (10)	−0.04467 (8)	0.68715 (6)	0.0336 (3)
N1	0.6323 (7)	−0.2005 (5)	0.6661 (4)	0.0317 (12)
N2	0.4854 (7)	0.1285 (6)	0.7313 (4)	0.0348 (13)
N3	0.7136 (6)	0.0320 (6)	0.7993 (4)	0.0297 (12)
C1	0.6124 (9)	−0.3014 (8)	0.5847 (6)	0.0432 (17)
H1	0.5523	−0.2989	0.5289	0.052*
C2	0.6782 (9)	−0.4073 (8)	0.5822 (7)	0.049 (2)
H2	0.6621	−0.4764	0.5254	0.059*
C3	0.7692 (9)	−0.4112 (8)	0.6646 (7)	0.052 (2)
H3	0.8124	−0.4838	0.6647	0.062*
C4	0.7945 (9)	−0.3049 (8)	0.7466 (6)	0.0446 (18)
H4	0.8582	−0.3038	0.8020	0.054*
C5	0.7259 (8)	−0.2022 (7)	0.7462 (5)	0.0347 (15)
C6	0.7397 (9)	−0.0843 (7)	0.8333 (5)	0.0366 (15)
H6A	0.6634	−0.1081	0.8760	0.044*
H6B	0.8426	−0.0615	0.8702	0.044*
C7	0.6546 (8)	0.1268 (8)	0.8735 (5)	0.0366 (15)
H7A	0.7411	0.1894	0.9182	0.044*
H7B	0.5876	0.0777	0.9110	0.044*
C8	0.5639 (8)	0.2029 (7)	0.8215 (5)	0.0312 (14)
C9	0.5518 (9)	0.3295 (8)	0.8604 (6)	0.0422 (17)
H9	0.6073	0.3782	0.9209	0.051*
C10	0.4567 (10)	0.3864 (8)	0.8099 (6)	0.0474 (19)
H10	0.4477	0.4734	0.8358	0.057*
C11	0.3760 (10)	0.3116 (8)	0.7210 (6)	0.0458 (18)
H11	0.3102	0.3469	0.6861	0.055*
C12	0.3937 (9)	0.1830 (7)	0.6836 (6)	0.0383 (16)
H12	0.3394	0.1333	0.6230	0.046*
C13	0.8563 (8)	0.1022 (7)	0.7620 (5)	0.0346 (15)
H13A	0.8870	0.0367	0.7118	0.041*
H13B	0.8284	0.1687	0.7315	0.041*
C14	0.9936 (8)	0.1705 (7)	0.8390 (5)	0.0330 (14)
C15	1.1037 (9)	0.1011 (8)	0.8615 (5)	0.0387 (16)
H15	1.0944	0.0129	0.8268	0.046*
C16	1.2250 (9)	0.1637 (10)	0.9350 (6)	0.0471 (19)
H16	1.2968	0.1167	0.9498	0.057*
C17	1.2425 (10)	0.2934 (10)	0.9867 (6)	0.054 (2)
H17	1.3240	0.3335	1.0372	0.065*
C18	1.1369 (10)	0.3654 (9)	0.9634 (7)	0.055 (2)
H18	1.1483	0.4543	0.9973	0.065*
C19	1.0152 (9)	0.3026 (8)	0.8891 (6)	0.0451 (18)
H19	0.9462	0.3511	0.8725	0.054*
S2	0.2877 (2)	−0.14702 (18)	0.48529 (12)	0.0348 (4)
O1	0.3536 (6)	−0.1334 (5)	0.5855 (4)	0.0395 (12)
O2	0.3152 (7)	−0.0226 (5)	0.4563 (4)	0.0420 (12)
O3	0.3108 (8)	−0.2602 (6)	0.4157 (4)	0.0530 (15)
C20	0.0783 (10)	−0.1903 (11)	0.4939 (6)	0.058 (2)
F1	0.0413 (7)	−0.1110 (8)	0.5697 (5)	0.091 (2)
F2	−0.0025 (6)	−0.1827 (8)	0.4137 (5)	0.089 (2)
F3	0.0329 (7)	−0.3163 (7)	0.5020 (5)	0.085 (2)
S3	0.2994 (2)	0.7737 (2)	0.84985 (14)	0.0389 (4)
O4	0.3741 (7)	0.8804 (5)	0.8071 (4)	0.0463 (13)
O5	0.4063 (7)	0.7232 (7)	0.9030 (4)	0.0568 (16)
O6	0.1665 (7)	0.7965 (6)	0.8955 (4)	0.0525 (15)
C21	0.2200 (8)	0.6361 (9)	0.7429 (6)	0.0428 (18)
F4	0.1218 (6)	0.6691 (6)	0.6824 (4)	0.0634 (14)
F5	0.1395 (7)	0.5273 (5)	0.7669 (4)	0.0686 (16)
F6	0.3303 (7)	0.5983 (5)	0.6925 (4)	0.0617 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0348 (5)	0.0315 (5)	0.0306 (4)	0.0087 (3)	−0.0046 (3)	0.0027 (3)
N1	0.034 (3)	0.023 (3)	0.030 (3)	0.007 (2)	0.000 (2)	−0.009 (2)
N2	0.037 (3)	0.039 (3)	0.027 (3)	0.006 (2)	0.000 (2)	0.009 (2)
N3	0.026 (3)	0.033 (3)	0.022 (3)	0.006 (2)	−0.005 (2)	−0.006 (2)
C1	0.042 (4)	0.040 (4)	0.045 (4)	0.009 (3)	0.001 (3)	0.007 (3)
C2	0.039 (4)	0.036 (4)	0.060 (5)	0.008 (3)	−0.004 (4)	−0.008 (4)
C3	0.039 (4)	0.034 (4)	0.078 (6)	0.011 (3)	−0.001 (4)	0.005 (4)
C4	0.042 (4)	0.039 (4)	0.053 (5)	0.012 (3)	−0.007 (3)	0.014 (3)
C5	0.026 (3)	0.034 (4)	0.041 (4)	0.004 (3)	−0.002 (3)	0.009 (3)
C6	0.038 (4)	0.038 (4)	0.038 (4)	0.009 (3)	0.000 (3)	0.017 (3)
C7	0.031 (3)	0.050 (4)	0.026 (3)	0.006 (3)	−0.002 (3)	0.009 (3)
C8	0.034 (3)	0.030 (3)	0.024 (3)	0.004 (3)	0.004 (3)	0.000 (2)
C9	0.038 (4)	0.041 (4)	0.040 (4)	0.008 (3)	0.004 (3)	−0.001 (3)
C10	0.051 (5)	0.035 (4)	0.055 (5)	0.015 (3)	0.000 (4)	0.008 (3)
C11	0.051 (5)	0.039 (4)	0.045 (4)	0.015 (4)	0.000 (4)	0.006 (3)
C12	0.040 (4)	0.033 (4)	0.047 (4)	0.021 (3)	−0.004 (3)	0.011 (3)
C13	0.038 (4)	0.042 (4)	0.024 (3)	0.014 (3)	−0.003 (3)	0.007 (3)
C14	0.035 (3)	0.029 (3)	0.031 (3)	0.005 (3)	0.003 (3)	0.004 (3)
C15	0.039 (4)	0.044 (4)	0.038 (4)	0.017 (3)	0.008 (3)	0.012 (3)
C16	0.028 (4)	0.073 (6)	0.043 (4)	0.014 (4)	0.001 (3)	0.021 (4)
C17	0.037 (4)	0.070 (6)	0.040 (4)	−0.002 (4)	0.000 (3)	0.001 (4)
C18	0.043 (5)	0.048 (5)	0.061 (5)	0.009 (4)	0.003 (4)	−0.007 (4)
C19	0.036 (4)	0.044 (4)	0.048 (4)	0.006 (3)	−0.004 (3)	0.004 (3)
S2	0.0354 (9)	0.0364 (9)	0.0288 (8)	0.0059 (7)	−0.0021 (6)	0.0055 (7)
O1	0.031 (3)	0.046 (3)	0.035 (3)	−0.001 (2)	−0.012 (2)	0.012 (2)
O2	0.056 (3)	0.039 (3)	0.033 (3)	0.017 (2)	−0.005 (2)	0.012 (2)
O3	0.072 (4)	0.036 (3)	0.042 (3)	0.009 (3)	0.004 (3)	−0.002 (2)
C20	0.042 (5)	0.085 (7)	0.042 (5)	0.005 (5)	−0.013 (4)	0.022 (5)
F1	0.064 (4)	0.148 (7)	0.075 (4)	0.048 (4)	0.027 (3)	0.029 (4)
F2	0.041 (3)	0.159 (7)	0.072 (4)	0.003 (3)	−0.011 (3)	0.065 (4)
F3	0.067 (4)	0.099 (5)	0.077 (4)	−0.023 (3)	−0.009 (3)	0.047 (4)
S3	0.0370 (9)	0.0432 (10)	0.0358 (9)	0.0098 (8)	0.0006 (7)	0.0102 (8)
O4	0.048 (3)	0.038 (3)	0.049 (3)	0.002 (2)	0.006 (3)	0.012 (2)
O5	0.050 (3)	0.077 (4)	0.050 (3)	0.025 (3)	−0.008 (3)	0.025 (3)
O6	0.046 (3)	0.065 (4)	0.051 (3)	0.020 (3)	0.017 (3)	0.016 (3)
C21	0.029 (4)	0.055 (5)	0.045 (4)	0.001 (3)	0.005 (3)	0.022 (4)
F4	0.056 (3)	0.075 (4)	0.054 (3)	0.007 (3)	−0.014 (2)	0.022 (3)
F5	0.078 (4)	0.045 (3)	0.079 (4)	−0.002 (3)	0.016 (3)	0.024 (3)
F6	0.068 (3)	0.052 (3)	0.062 (3)	0.015 (3)	0.023 (3)	0.005 (2)

Geometric parameters (Å, º)

Cu1—O1	1.997 (5)	C13—C14	1.501 (9)
Cu1—N1	1.979 (5)	C14—C19	1.374 (10)
Cu1—N2	1.959 (6)	C14—C15	1.405 (10)
Cu1—N3	2.027 (5)	C15—C16	1.374 (11)
N1—C1	1.347 (9)	C16—C17	1.364 (13)
N1—C5	1.364 (9)	C17—C18	1.397 (13)
N2—C12	1.326 (8)	C18—C19	1.383 (11)
N2—C8	1.379 (8)	S2—O3	1.426 (6)
N3—C6	1.475 (9)	S2—O2	1.440 (5)
N3—C7	1.485 (9)	S2—O1	1.458 (5)
N3—C13	1.516 (9)	S2—C20	1.834 (9)
C1—C2	1.366 (11)	C20—F1	1.311 (12)
C2—C3	1.385 (12)	C20—F2	1.328 (9)
C3—C4	1.381 (12)	C20—F3	1.336 (12)
C4—C5	1.357 (10)	S3—O6	1.426 (6)
C5—C6	1.512 (10)	S3—O5	1.434 (6)
C7—C8	1.519 (10)	S3—O4	1.455 (6)
C8—C9	1.353 (10)	S3—C21	1.811 (9)
C9—C10	1.386 (11)	C21—F6	1.330 (9)
C10—C11	1.373 (11)	C21—F4	1.334 (9)
C11—C12	1.386 (10)	C21—F5	1.341 (9)
N2—Cu1—N1	166.8 (2)	C14—C13—N3	114.6 (5)
N2—Cu1—O1	97.7 (2)	C19—C14—C15	118.3 (7)
N1—Cu1—O1	95.5 (2)	C19—C14—C13	120.9 (7)
N2—Cu1—N3	84.3 (2)	C15—C14—C13	120.8 (6)
N1—Cu1—N3	82.5 (2)	C16—C15—C14	119.9 (7)
O1—Cu1—N3	173.7 (2)	C17—C16—C15	121.4 (8)
C1—N1—C5	118.8 (6)	C16—C17—C18	119.5 (8)
C1—N1—Cu1	127.8 (5)	C19—C18—C17	119.1 (8)
C5—N1—Cu1	113.4 (4)	C14—C19—C18	121.7 (8)
C12—N2—C8	118.3 (6)	O3—S2—O2	116.0 (3)
C12—N2—Cu1	128.3 (5)	O3—S2—O1	114.4 (3)
C8—N2—Cu1	113.3 (5)	O2—S2—O1	114.0 (3)
C6—N3—C7	112.9 (5)	O3—S2—C20	103.9 (4)
C6—N3—C13	111.9 (5)	O2—S2—C20	104.9 (4)
C7—N3—C13	112.0 (5)	O1—S2—C20	101.5 (3)
C6—N3—Cu1	105.4 (4)	S2—O1—Cu1	144.8 (3)
C7—N3—Cu1	105.1 (4)	F1—C20—F2	108.4 (9)
C13—N3—Cu1	108.9 (4)	F1—C20—F3	107.9 (8)
N1—C1—C2	121.5 (7)	F2—C20—F3	107.3 (8)
C1—C2—C3	119.6 (8)	F1—C20—S2	112.1 (6)
C4—C3—C2	118.6 (7)	F2—C20—S2	110.5 (7)
C5—C4—C3	119.8 (7)	F3—C20—S2	110.4 (7)
C4—C5—N1	121.5 (7)	O6—S3—O5	115.9 (4)
C4—C5—C6	124.1 (7)	O6—S3—O4	114.5 (4)
N1—C5—C6	114.3 (6)	O5—S3—O4	114.0 (4)
N3—C6—C5	109.6 (6)	O6—S3—C21	104.2 (4)
N3—C7—C8	109.0 (5)	O5—S3—C21	103.5 (4)
C9—C8—N2	121.7 (7)	O4—S3—C21	102.4 (3)
C9—C8—C7	124.4 (6)	F6—C21—F4	107.7 (7)
N2—C8—C7	113.9 (6)	F6—C21—F5	106.9 (7)
C8—C9—C10	119.9 (7)	F4—C21—F5	106.6 (6)
C11—C10—C9	118.6 (7)	F6—C21—S3	112.2 (5)
C10—C11—C12	119.4 (7)	F4—C21—S3	111.3 (6)
N2—C12—C11	122.2 (7)	F5—C21—S3	111.7 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O5^i	0.93	2.70	3.633	176
C3—H3···O3^ii	0.93	2.63	3.286	128
C11—H11···F6^i	0.93	2.60	3.251	127

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