The title compound, (I), [Cu(trifacac)2(DabcoCH2Cl)](BF4)2 or [Cu(C5H4F3O2)2(C7H14ClN2)2](BF4)2 (Dabco is diazabicyclo[2.2.2]octane and trifacac is trifluoroacetylacetonate) was synthesized from the reaction of Selectfluor [Selectfluor is 1-(chloromethyl)-4-fluoro-1,4-diazobicyclo[2.2.2]octane bis(tetrafluoroborate)] and Cu(trifacac)2. The central Cu atom is octahedrally coordinated by two N(CH2CH2)3NCH2Cl+ and two trifacac ligands in a trans conformation. The Cu atom is located on a center of symmetry. The Cu—N and Cu—O distances are 2.5514 (19) and 1.9550 (15), 1.9592 (15) Å.
Supporting information
CCDC reference: 200736
Key indicators
- Single-crystal X-ray study
- T = 203 K
- Mean (C-C) = 0.003 Å
- R factor = 0.040
- wR factor = 0.110
- Data-to-parameter ratio = 17.1
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: XS in SHELXTL (Sheldrick, 1998); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.
Crystal data top
[Cu(C5H4F3O2)2(C7H14ClN2)2](BF4)2 | F(000) = 878 |
Mr = 866.63 | Dx = 1.725 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.0098 (12) Å | Cell parameters from 993 reflections |
b = 15.1046 (18) Å | θ = 2.3–28.2° |
c = 11.5086 (14) Å | µ = 0.93 mm−1 |
β = 106.50 (2)° | T = 203 K |
V = 1668.4 (3) Å3 | Needle, pale green |
Z = 2 | 0.60 × 0.25 × 0.13 mm |
Data collection top
Bruker–Siemens SMART 1K diffractometer | 3984 independent reflections |
Radiation source: normal-focus sealed tube | 3155 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 8.3 pixels mm-1 | θmax = 28.3°, θmin = 2.3° |
ω scans | h = −13→13 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1999) | k = −18→19 |
Tmin = 0.605, Tmax = 0.888 | l = −10→15 |
12231 measured reflections | |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0628P)2 + 0.6096P] where P = (Fo2 + 2Fc2)/3 |
3984 reflections | (Δ/σ)max < 0.001 |
233 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
B1 | 0.2079 (3) | 0.1265 (2) | 0.0472 (3) | 0.0403 (7) | |
C1 | 0.7561 (2) | −0.05121 (14) | 0.56397 (19) | 0.0220 (4) | |
Cl1 | 0.56071 (7) | 0.15429 (5) | −0.11653 (6) | 0.03853 (17) | |
Cu1 | 1.0000 | 0.0000 | 0.5000 | 0.02212 (12) | |
F1 | 0.67556 (16) | −0.19566 (9) | 0.58291 (15) | 0.0404 (4) | |
N1 | 0.83990 (19) | 0.07461 (12) | 0.31309 (17) | 0.0255 (4) | |
O1 | 0.84246 (15) | −0.07439 (10) | 0.50653 (14) | 0.0237 (3) | |
C2 | 0.6326 (2) | −0.11524 (15) | 0.5415 (2) | 0.0274 (5) | |
F2 | 0.56977 (15) | −0.12368 (10) | 0.42243 (14) | 0.0407 (4) | |
N2 | 0.67670 (18) | 0.15257 (12) | 0.12796 (16) | 0.0232 (4) | |
O2 | 0.96487 (15) | 0.08689 (10) | 0.61427 (14) | 0.0250 (3) | |
C3 | 0.7607 (2) | 0.01914 (15) | 0.6394 (2) | 0.0271 (5) | |
H3A | 0.6883 | 0.0254 | 0.6759 | 0.032* | |
F3 | 0.53414 (15) | −0.09041 (11) | 0.59256 (16) | 0.0430 (4) | |
C4 | 0.8689 (2) | 0.08367 (14) | 0.6658 (2) | 0.0255 (5) | |
F4 | 0.2355 (2) | 0.15530 (16) | −0.0567 (2) | 0.0779 (7) | |
C5 | 0.8700 (3) | 0.15131 (19) | 0.7600 (3) | 0.0453 (7) | |
H5A | 0.9656 | 0.1662 | 0.8030 | 0.068* | |
H5B | 0.8236 | 0.1278 | 0.8167 | 0.068* | |
H5C | 0.8217 | 0.2040 | 0.7218 | 0.068* | |
F5 | 0.1693 (4) | 0.03928 (19) | 0.0313 (3) | 0.1206 (11) | |
C6 | 0.7802 (3) | 0.15455 (16) | 0.3506 (2) | 0.0312 (5) | |
H6A | 0.8547 | 0.1975 | 0.3837 | 0.037* | |
H6B | 0.7376 | 0.1393 | 0.4149 | 0.037* | |
F6 | 0.1053 (2) | 0.17137 (19) | 0.0748 (3) | 0.0925 (8) | |
C7 | 0.6697 (3) | 0.19699 (16) | 0.2443 (2) | 0.0324 (5) | |
H7A | 0.5768 | 0.1892 | 0.2552 | 0.039* | |
H7B | 0.6877 | 0.2606 | 0.2408 | 0.039* | |
F7 | 0.3282 (2) | 0.1318 (2) | 0.1411 (2) | 0.0929 (8) | |
C8 | 0.7245 (3) | 0.01555 (15) | 0.2512 (2) | 0.0341 (6) | |
H8A | 0.6662 | 0.0037 | 0.3050 | 0.041* | |
H8B | 0.7625 | −0.0410 | 0.2335 | 0.041* | |
C9 | 0.6344 (2) | 0.05671 (15) | 0.1325 (2) | 0.0299 (5) | |
H9A | 0.6482 | 0.0244 | 0.0630 | 0.036* | |
H9B | 0.5357 | 0.0530 | 0.1293 | 0.036* | |
C10 | 0.9156 (2) | 0.09994 (19) | 0.2260 (2) | 0.0351 (6) | |
H10A | 0.9465 | 0.0463 | 0.1931 | 0.042* | |
H10B | 0.9986 | 0.1339 | 0.2680 | 0.042* | |
C11 | 0.8251 (2) | 0.15566 (18) | 0.1210 (2) | 0.0331 (5) | |
H11A | 0.8585 | 0.2170 | 0.1277 | 0.040* | |
H11B | 0.8302 | 0.1317 | 0.0432 | 0.040* | |
C12 | 0.5778 (2) | 0.20234 (16) | 0.0269 (2) | 0.0291 (5) | |
H12A | 0.6108 | 0.2634 | 0.0266 | 0.035* | |
H12B | 0.4861 | 0.2043 | 0.0416 | 0.035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
B1 | 0.0353 (15) | 0.0491 (18) | 0.0398 (17) | −0.0044 (13) | 0.0161 (13) | −0.0023 (14) |
C1 | 0.0198 (9) | 0.0238 (10) | 0.0228 (11) | 0.0014 (8) | 0.0068 (8) | 0.0053 (8) |
Cl1 | 0.0369 (3) | 0.0508 (4) | 0.0250 (3) | 0.0042 (3) | 0.0042 (2) | 0.0052 (3) |
Cu1 | 0.02141 (19) | 0.02276 (19) | 0.0256 (2) | −0.00156 (14) | 0.01210 (15) | −0.00335 (15) |
F1 | 0.0447 (8) | 0.0273 (7) | 0.0518 (10) | −0.0034 (6) | 0.0180 (7) | 0.0085 (7) |
N1 | 0.0239 (9) | 0.0261 (10) | 0.0251 (10) | −0.0003 (7) | 0.0048 (7) | 0.0031 (8) |
O1 | 0.0237 (7) | 0.0248 (8) | 0.0254 (8) | −0.0011 (6) | 0.0114 (6) | −0.0026 (6) |
C2 | 0.0253 (11) | 0.0280 (11) | 0.0307 (12) | 0.0001 (9) | 0.0105 (9) | 0.0000 (9) |
F2 | 0.0338 (8) | 0.0495 (9) | 0.0347 (8) | −0.0124 (7) | 0.0032 (6) | −0.0024 (7) |
N2 | 0.0204 (8) | 0.0244 (9) | 0.0233 (9) | 0.0011 (7) | 0.0038 (7) | 0.0039 (7) |
O2 | 0.0247 (7) | 0.0259 (8) | 0.0269 (8) | −0.0008 (6) | 0.0114 (6) | −0.0028 (6) |
C3 | 0.0241 (11) | 0.0307 (12) | 0.0306 (12) | −0.0003 (8) | 0.0146 (9) | −0.0033 (9) |
F3 | 0.0301 (7) | 0.0491 (9) | 0.0582 (10) | −0.0077 (6) | 0.0261 (7) | −0.0095 (8) |
C4 | 0.0263 (11) | 0.0261 (11) | 0.0263 (11) | 0.0031 (8) | 0.0108 (9) | 0.0002 (9) |
F4 | 0.0703 (14) | 0.1094 (18) | 0.0596 (13) | −0.0070 (12) | 0.0276 (11) | 0.0247 (12) |
C5 | 0.0470 (15) | 0.0444 (16) | 0.0545 (18) | −0.0132 (12) | 0.0308 (14) | −0.0229 (13) |
F5 | 0.182 (3) | 0.0709 (17) | 0.135 (3) | −0.0474 (19) | 0.086 (2) | −0.0223 (17) |
C6 | 0.0318 (12) | 0.0331 (12) | 0.0257 (12) | 0.0034 (9) | 0.0032 (10) | −0.0030 (9) |
F6 | 0.0580 (13) | 0.124 (2) | 0.105 (2) | 0.0286 (13) | 0.0383 (13) | −0.0027 (16) |
C7 | 0.0386 (13) | 0.0297 (12) | 0.0269 (12) | 0.0074 (10) | 0.0059 (10) | −0.0019 (10) |
F7 | 0.0428 (11) | 0.171 (3) | 0.0604 (14) | −0.0039 (13) | 0.0070 (10) | 0.0002 (15) |
C8 | 0.0397 (14) | 0.0260 (12) | 0.0296 (13) | −0.0066 (9) | −0.0014 (11) | 0.0057 (9) |
C9 | 0.0289 (11) | 0.0264 (11) | 0.0296 (12) | −0.0049 (9) | 0.0006 (9) | 0.0034 (9) |
C10 | 0.0237 (11) | 0.0474 (15) | 0.0345 (14) | 0.0086 (10) | 0.0087 (10) | 0.0141 (11) |
C11 | 0.0205 (11) | 0.0453 (14) | 0.0329 (13) | 0.0012 (9) | 0.0067 (9) | 0.0140 (11) |
C12 | 0.0268 (11) | 0.0317 (12) | 0.0268 (12) | 0.0049 (9) | 0.0044 (9) | 0.0066 (9) |
Geometric parameters (Å, º) top
B1—F6 | 1.342 (4) | C3—C4 | 1.424 (3) |
B1—F5 | 1.370 (4) | C3—H3A | 0.9400 |
B1—F4 | 1.372 (4) | C4—C5 | 1.488 (3) |
B1—F7 | 1.373 (4) | C5—H5A | 0.9700 |
C1—O1 | 1.278 (3) | C5—H5B | 0.9700 |
C1—C3 | 1.364 (3) | C5—H5C | 0.9700 |
C1—C2 | 1.533 (3) | C6—C7 | 1.537 (3) |
Cl1—C12 | 1.767 (2) | C6—H6A | 0.9800 |
Cu1—O1 | 1.9550 (15) | C6—H6B | 0.9800 |
Cu1—O1i | 1.9550 (15) | C7—H7A | 0.9800 |
Cu1—O2i | 1.9591 (15) | C7—H7B | 0.9800 |
Cu1—O2 | 1.9591 (15) | C8—C9 | 1.538 (3) |
F1—C2 | 1.331 (3) | C8—H8A | 0.9800 |
N1—C6 | 1.466 (3) | C8—H8B | 0.9800 |
N1—C10 | 1.469 (3) | C9—H9A | 0.9800 |
N1—C8 | 1.473 (3) | C9—H9B | 0.9800 |
C2—F3 | 1.336 (3) | C10—C11 | 1.538 (3) |
C2—F2 | 1.341 (3) | C10—H10A | 0.9800 |
N2—C12 | 1.497 (3) | C10—H10B | 0.9800 |
N2—C11 | 1.511 (3) | C11—H11A | 0.9800 |
N2—C9 | 1.514 (3) | C11—H11B | 0.9800 |
N2—C7 | 1.517 (3) | C12—H12A | 0.9800 |
O2—C4 | 1.265 (3) | C12—H12B | 0.9800 |
| | | |
F6—B1—F5 | 108.1 (3) | H5B—C5—H5C | 109.5 |
F6—B1—F4 | 113.8 (3) | N1—C6—C7 | 111.74 (19) |
F5—B1—F4 | 107.9 (3) | N1—C6—H6A | 109.3 |
F6—B1—F7 | 110.1 (3) | C7—C6—H6A | 109.3 |
F5—B1—F7 | 108.2 (3) | N1—C6—H6B | 109.3 |
F4—B1—F7 | 108.6 (3) | C7—C6—H6B | 109.3 |
O1—C1—C3 | 129.6 (2) | H6A—C6—H6B | 107.9 |
O1—C1—C2 | 111.83 (19) | N2—C7—C6 | 108.38 (18) |
C3—C1—C2 | 118.61 (19) | N2—C7—H7A | 110.0 |
O1—Cu1—O1i | 180.0 | C6—C7—H7A | 110.0 |
O1—Cu1—O2i | 86.64 (6) | N2—C7—H7B | 110.0 |
O1i—Cu1—O2i | 93.36 (6) | C6—C7—H7B | 110.0 |
O1—Cu1—O2 | 93.36 (6) | H7A—C7—H7B | 108.4 |
O1i—Cu1—O2 | 86.64 (6) | N1—C8—C9 | 111.45 (18) |
O2i—Cu1—O2 | 180.00 (7) | N1—C8—H8A | 109.3 |
C6—N1—C10 | 108.62 (19) | C9—C8—H8A | 109.3 |
C6—N1—C8 | 108.16 (18) | N1—C8—H8B | 109.3 |
C10—N1—C8 | 108.3 (2) | C9—C8—H8B | 109.3 |
C1—O1—Cu1 | 122.30 (14) | H8A—C8—H8B | 108.0 |
F1—C2—F3 | 107.59 (19) | N2—C9—C8 | 108.57 (18) |
F1—C2—F2 | 106.81 (19) | N2—C9—H9A | 110.0 |
F3—C2—F2 | 106.61 (19) | C8—C9—H9A | 110.0 |
F1—C2—C1 | 110.62 (18) | N2—C9—H9B | 110.0 |
F3—C2—C1 | 114.12 (19) | C8—C9—H9B | 110.0 |
F2—C2—C1 | 110.73 (18) | H9A—C9—H9B | 108.4 |
C12—N2—C11 | 112.72 (17) | N1—C10—C11 | 112.09 (19) |
C12—N2—C9 | 112.18 (17) | N1—C10—H10A | 109.2 |
C11—N2—C9 | 108.67 (18) | C11—C10—H10A | 109.2 |
C12—N2—C7 | 106.11 (17) | N1—C10—H10B | 109.2 |
C11—N2—C7 | 109.01 (18) | C11—C10—H10B | 109.2 |
C9—N2—C7 | 107.99 (18) | H10A—C10—H10B | 107.9 |
C4—O2—Cu1 | 126.42 (14) | N2—C11—C10 | 108.04 (18) |
C1—C3—C4 | 123.7 (2) | N2—C11—H11A | 110.1 |
C1—C3—H3A | 118.1 | C10—C11—H11A | 110.1 |
C4—C3—H3A | 118.1 | N2—C11—H11B | 110.1 |
O2—C4—C3 | 124.0 (2) | C10—C11—H11B | 110.1 |
O2—C4—C5 | 117.7 (2) | H11A—C11—H11B | 108.4 |
C3—C4—C5 | 118.3 (2) | N2—C12—Cl1 | 112.75 (16) |
C4—C5—H5A | 109.5 | N2—C12—H12A | 109.0 |
C4—C5—H5B | 109.5 | Cl1—C12—H12A | 109.0 |
H5A—C5—H5B | 109.5 | N2—C12—H12B | 109.0 |
C4—C5—H5C | 109.5 | Cl1—C12—H12B | 109.0 |
H5A—C5—H5C | 109.5 | H12A—C12—H12B | 107.8 |
Symmetry code: (i) −x+2, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···F4 | 0.98 | 2.55 | 3.362 (3) | 140 |
C9—H9B···F7 | 0.98 | 2.43 | 3.296 (3) | 147 |
C12—H12B···F7 | 0.98 | 2.46 | 3.312 (3) | 146 |
C12—H12A···O1ii | 0.98 | 2.54 | 3.512 (3) | 170 |
Symmetry code: (ii) −x+3/2, y+1/2, −z+1/2. |
A comparison of the Cu—N distances and angles between compound (I) and
reported values in the CSD (Å, °). topRefcode | Cu—N | N—Cu—N |
(I) | 2.5514 (19) | 180.00 |
HOYZIE | 2.389 (5) | 180.00 |
KOWFIL | 2.545 (4) | 180.00 |
LECWEV | 2.537 (10) | 180.00 |
QOTMUH | 2.445 (2) | 180.00 |