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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-κ
3N,
N′,
N′′)bis(trifluoromethanesulfonato-κ
O)copper(II) tetrahydrofuran monosolvate, [Cu(CF
3SO
3)
2(C
19H
19N
3)(H
2O)]·C
4H
8O, (I), and a triflate-bridged Cu
II dinuclear complex, bis(μ-trifluoromethanesulfonato-κ
2O:
O′)bis[(benzyldipicolylamine-κ
3N,
N′,
N′′)(trifluoromethanesulfonato-κ
O)copper(II)], [Cu
2(CF
3SO
3)
4(C
19H
19N
3)
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.
Supporting information
CCDC references: 1561680; 1561883
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)
top
Crystal data top
[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) Å3 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.73 | w = 1/[σ2(Fo2) + (0.0173P)2] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.84 | 1.94 | 2.719 (5) | 153 |
O1—H1B···O8ii | 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)
top
Crystal data top
[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) Å3 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.259 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0728P)2 + 10.1901P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O5i | 0.93 | 2.70 | 3.633 | 176 |
C3—H3···O3ii | 0.93 | 2.63 | 3.286 | 128 |
C11—H11···F6i | 0.93 | 2.60 | 3.251 | 127 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1. |
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