Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103016743/sk1648sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103016743/sk1648Xsup2.hkl |
CCDC reference: 224498
To a solution of cyclam (0.5 mmol) in ethanol (10 ml) was added Cu(ClO4)2·6H2O (0.5 mmol) in H2O (5 ml), followed by Na[B{C6H3(CF3)3-3,5}4] (1 mmol) in Me2CO (5 ml). The reaction mixture was left overnight, and then the solvent was evaporated and the residue was recrystallized from MeCN/Et2O. Purple crystals of [Cu(cyclam)(MeCN)2][B{C6H3(CF3)3-3,5}4]·0.31H2O (m.p. 481–483 K) formed slowly.
The structures were solved using Patterson methods (SHELXS86) in the orthorhombic spacegroup Cmca and refined by least-squares using SHELXL97, both programs running within OSCAIL for Windows (McArdle, 1994, 2002). H atoms were refined using a riding model employing the appropriate AFIX commands of SHELXL97. The H atom on water molecule O31 could not be located because the amount of water in the structure is small. However, the assignment of water at this location is justified because of the solvent- accessible areas identified by PLATON (50 Å3 / Void) (Spek, 2003).
1,4,8,11-Tetraazacyclotetradecane (cyclam) and its derivatives have been studied extensively as ligands for transition metal complexes, including copper compounds. Among the copper(II)–cyclam complexes whose crystal structures have been reported are neutral complexes, such as [CuII(cyclam)(SC6F5)2], (I) [Cambridge Structural Database (Allen, 2002) refcode BUTYUK; Addison & Sinn, 1983], [CuII(cyclam)Br2], (II) (TEGPOK; Chen et al., 1996; see also Matsuo et al., 2001), and [CuII(cyclam)(ClO4)2], (III) (PTZDCU; Taskar & Sklar, 1975), and ionic complexes, for example [CuII(cyclam)(H2O)2][F(H2O)4]2, (IV) (JABSUA10; Emsley et al., 1990; see also Matsuo et al., 2001), [CuII(cyclam)][CuIBr3], (V) (QIWVAT; Willett & Vij, 2000), [CuIICl(cyclam)]2[CdCl4], (VI) (YUMBUD; Pickardt & Hoffmeister, 1995), [CuII(cyclam)][CdCl3(H2O)2]Cl, (VII) (YUMCAK; Pickardt & Hoffmeister, 1995), [CuII(NCS)(cyclam)][SCN], (VIII) (ZUZJUZ; Lu et al., 1996) and [CuII(cyclam)][BH4]2, (IX) (HAFSUC; Antsyshkina et al., 1992). In complexes (I)–(VII), copper is six-coordinated, with the four N atoms of the cyclam ligand in the equatorial sites of a distorted octahedral structures. The axial ligands in (I)–(IV) are the other bound ligands [SC6F5 in (I), Br in (II), OClO3 in (III) and OH2 in (IV)], while in (V)–(VII), the axial sites are occupied by halides, including bridging ligands from the halometallete anions. In contrast to the situation in (I)–(VII), the Cu centre in (VIII) has essentially a distorted square-pyramidal geometry, with the bound isothiocyanate ligand in the axial site; however, there is also a weak Cu···S interaction with a neighbouring cation, at a distance only ca 0.185 Å less than the sum of the van der Waals radii.
In order to study the effect of a large non-interacting anion on the structure of a copper(II)–cyclam complex, a complex with the [B{C6H3(CF3)2-3,5}4] anion was sought. The title compound, (X), was obtained on recrystallizing the reaction product from cyclam, Cu(ClO4)2·6H2O and Na[B{C6H3(CF3)2-3,5}4] from MeCN/Et2O solution.
Complex (X), in space group Cmca, exists as an ionic species with no interactions between the distorted octahedral [CuII(cyclam)(NCMe)2]2+ dications (Figs. 1a and 1 b) and the distorted tetrahedral [B{C6H3(CF3)-3,5}4]-1 anions (Fig. 1c). The arrangement of these molecules in the unit cell is shown in Fig. 2. As in complexes (I)–(VII), the equatorial sites in the dication of (X) are occupied by the four cyclam N atoms; the uniform Cu—Ncyclam bond length is 2.013 (2) Å and is within the range found in the other Cu(cyclam) complexes. The axial Cu—Nacetonitrile bond lengths are much longer [2.499 (4) Å]. The distortion from an ideal octahedral geometry is small, as shown by the N—Cu—N bond angles (Table 1). The equatorial N—Cu—N angles [N1—Cu1—N1i and N1ii—Cu1—N1iii] within the five-membered rings are, as expected, smaller than those within the six-membered rings [N1—Cu1—N1iii and N1i—Cu1—N1ii], viz. 86.05 (9) versus 93.95 (9)°, respectively. The Naxial—Cu—Nequatorial angles are 93.55 (9) and 86.45 (9)°, with an Naxial—Cu—Naxial angle of 180°. The Cu—N≡C(Me) fragment is nearly linear [Cu1—N31—C32 = 166.3 (3)°], and the terminal methyl group is disordered. The configurations of the four chiral N centres in (X) are 1RS, 4RS, 8SR and 11SR. On th basis off the puckering parameters of Cremer & Pople (1975), the six-membered chelate rings have near chair-shaped conformations [Q = 0.591 (4) Å, θ = 12.6 (3)° and φ = 180.0 (14)°], while the five-membered rings have twist conformations [Q = 0.454 (3) Å and φ = 270.0 (3)°].
The C—B—C bond angles in the anion of (X) are clustered around the ideal tetrahedral angle of 109.5°, being between 105.7 (2) and 113.04 (11)°.
Water molecules are disordered between columns of anions, which form parallel to (011) (Figure 2c), with approximately one-third of a water atom present in the formula unit.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX in OSCAIL (McArdle, 1994, 2000) and ORTEPIII for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Cu(C2H3N)2(C10H24N4)](C32H12BF24)2·0.31H2O | F(000) = 4150.2 |
Mr = 2077.43 | Dx = 1.666 Mg m−3 |
Orthorhombic, Cmca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2bc 2 | Cell parameters from 26477 reflections |
a = 25.7320 (6) Å | θ = 2.9–27.5° |
b = 18.3516 (4) Å | µ = 0.42 mm−1 |
c = 17.5412 (4) Å | T = 120 K |
V = 8283.4 (3) Å3 | Block, purple |
Z = 4 | 0.22 × 0.12 × 0.04 mm |
Nonius KappaCCD diffractometer | 4855 independent reflections |
Radiation source: Rotating Anode | 3525 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
φ–ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) | h = −33→25 |
Tmin = 0.920, Tmax = 0.983 | k = −22→23 |
32892 measured reflections | l = −22→22 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0731P)2 + 12.7378P] where P = (Fo2 + 2Fc2)/3 |
4855 reflections | (Δ/σ)max < 0.001 |
315 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Cu(C2H3N)2(C10H24N4)](C32H12BF24)2·0.31H2O | V = 8283.4 (3) Å3 |
Mr = 2077.43 | Z = 4 |
Orthorhombic, Cmca | Mo Kα radiation |
a = 25.7320 (6) Å | µ = 0.42 mm−1 |
b = 18.3516 (4) Å | T = 120 K |
c = 17.5412 (4) Å | 0.22 × 0.12 × 0.04 mm |
Nonius KappaCCD diffractometer | 4855 independent reflections |
Absorption correction: empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) | 3525 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 0.983 | Rint = 0.072 |
32892 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0731P)2 + 12.7378P] where P = (Fo2 + 2Fc2)/3 |
4855 reflections | Δρmax = 0.64 e Å−3 |
315 parameters | Δρmin = −0.37 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.5000 | 0.0000 | 0.0000 | 0.02293 (16) | |
N1 | 0.44280 (9) | 0.04606 (13) | 0.06174 (13) | 0.0339 (5) | |
H1 | 0.4390 | 0.0933 | 0.0434 | 0.041* | |
C1 | 0.39428 (10) | 0.00774 (15) | 0.04332 (16) | 0.0333 (6) | |
H1A | 0.3640 | 0.0382 | 0.0571 | 0.040* | |
H1B | 0.3922 | −0.0385 | 0.0722 | 0.040* | |
C2 | 0.45024 (12) | 0.05253 (19) | 0.14503 (17) | 0.0443 (7) | |
H2A | 0.4522 | 0.0033 | 0.1679 | 0.053* | |
H2B | 0.4201 | 0.0781 | 0.1677 | 0.053* | |
C3 | 0.5000 | 0.0945 (3) | 0.1635 (3) | 0.0504 (11) | |
H3A | 0.5000 | 0.1069 | 0.2184 | 0.060* | |
H3B | 0.5000 | 0.1407 | 0.1345 | 0.060* | |
B1 | 0.2500 | 0.64348 (19) | 0.2500 | 0.0178 (7) | |
C11 | 0.29149 (9) | 0.69759 (11) | 0.29332 (12) | 0.0187 (4) | |
C12 | 0.31700 (9) | 0.75119 (12) | 0.25017 (12) | 0.0199 (5) | |
H12 | 0.3085 | 0.7561 | 0.1977 | 0.024* | |
C13 | 0.35395 (9) | 0.79700 (12) | 0.28111 (13) | 0.0217 (5) | |
C14 | 0.36677 (9) | 0.79302 (12) | 0.35817 (13) | 0.0223 (5) | |
H14 | 0.3924 | 0.8242 | 0.3797 | 0.027* | |
C15 | 0.34088 (9) | 0.74208 (12) | 0.40233 (12) | 0.0211 (5) | |
C16 | 0.30444 (9) | 0.69500 (12) | 0.37071 (13) | 0.0197 (5) | |
H16 | 0.2879 | 0.6601 | 0.4025 | 0.024* | |
C17 | 0.38008 (11) | 0.85290 (14) | 0.23253 (14) | 0.0296 (6) | |
F11 | 0.35545 (8) | 0.91710 (8) | 0.23218 (10) | 0.0504 (5) | |
F12 | 0.38353 (7) | 0.83278 (9) | 0.15960 (8) | 0.0403 (4) | |
F13 | 0.42874 (7) | 0.86717 (11) | 0.25527 (10) | 0.0510 (5) | |
C18 | 0.35328 (10) | 0.73643 (13) | 0.48517 (13) | 0.0252 (5) | |
F14 | 0.38030 (7) | 0.79280 (9) | 0.51200 (8) | 0.0437 (4) | |
F15 | 0.38192 (7) | 0.67615 (10) | 0.50021 (9) | 0.0466 (5) | |
F16 | 0.31149 (6) | 0.73061 (9) | 0.52933 (8) | 0.0350 (4) | |
C21 | 0.21851 (9) | 0.58979 (12) | 0.30894 (12) | 0.0183 (4) | |
C22 | 0.16539 (9) | 0.59505 (12) | 0.32421 (13) | 0.0213 (5) | |
H22 | 0.1464 | 0.6343 | 0.3026 | 0.026* | |
C23 | 0.13929 (9) | 0.54502 (12) | 0.36979 (13) | 0.0212 (5) | |
C24 | 0.16527 (9) | 0.48732 (12) | 0.40312 (13) | 0.0210 (5) | |
H24 | 0.1475 | 0.4534 | 0.4347 | 0.025* | |
C25 | 0.21805 (9) | 0.48064 (12) | 0.38895 (12) | 0.0195 (5) | |
C26 | 0.24390 (9) | 0.53058 (12) | 0.34305 (12) | 0.0185 (4) | |
H26 | 0.2801 | 0.5244 | 0.3345 | 0.022* | |
C27 | 0.08214 (10) | 0.55161 (14) | 0.38251 (14) | 0.0273 (5) | |
F21 | 0.05970 (6) | 0.60122 (13) | 0.33821 (12) | 0.0637 (6) | |
F22 | 0.05743 (7) | 0.48945 (10) | 0.37274 (15) | 0.0657 (6) | |
F23 | 0.07033 (7) | 0.57232 (12) | 0.45354 (10) | 0.0531 (5) | |
C28 | 0.24668 (9) | 0.41599 (12) | 0.41923 (13) | 0.0227 (5) | |
F24 | 0.22124 (6) | 0.38141 (7) | 0.47486 (8) | 0.0312 (3) | |
F25 | 0.29335 (6) | 0.43367 (8) | 0.44801 (10) | 0.0379 (4) | |
F26 | 0.25586 (6) | 0.36644 (8) | 0.36494 (8) | 0.0333 (4) | |
N31 | 0.5000 | −0.1145 (2) | 0.0771 (2) | 0.0403 (8) | |
C32 | 0.5000 | −0.1723 (2) | 0.0980 (2) | 0.0396 (9) | |
C33 | 0.5000 | −0.2471 (3) | 0.1248 (4) | 0.0670 (15) | |
H33A | 0.5356 | −0.2661 | 0.1242 | 0.101* | 0.50 |
H33B | 0.4781 | −0.2768 | 0.0913 | 0.101* | 0.50 |
H33C | 0.4863 | −0.2488 | 0.1769 | 0.101* | 0.50 |
O31 | 0.0000 | 0.3469 (3) | 0.4174 (4) | 0.062 (6)* | 0.16 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0168 (3) | 0.0269 (3) | 0.0252 (3) | 0.000 | 0.000 | 0.0040 (2) |
N1 | 0.0286 (12) | 0.0345 (12) | 0.0387 (12) | 0.0008 (9) | 0.0009 (10) | 0.0038 (10) |
C1 | 0.0216 (12) | 0.0341 (14) | 0.0442 (16) | 0.0022 (11) | 0.0028 (11) | 0.0114 (12) |
C2 | 0.0401 (17) | 0.0582 (19) | 0.0344 (15) | 0.0008 (14) | 0.0088 (13) | −0.0005 (14) |
C3 | 0.039 (2) | 0.070 (3) | 0.041 (2) | 0.000 | 0.000 | −0.013 (2) |
B1 | 0.0213 (18) | 0.0167 (16) | 0.0155 (16) | 0.000 | −0.0007 (13) | 0.000 |
C11 | 0.0192 (11) | 0.0176 (10) | 0.0193 (10) | 0.0028 (9) | 0.0013 (8) | −0.0008 (8) |
C12 | 0.0235 (11) | 0.0211 (10) | 0.0150 (10) | 0.0013 (9) | 0.0003 (9) | −0.0006 (8) |
C13 | 0.0243 (12) | 0.0211 (11) | 0.0198 (11) | −0.0003 (10) | 0.0015 (9) | −0.0005 (9) |
C14 | 0.0249 (12) | 0.0213 (11) | 0.0208 (11) | −0.0034 (10) | −0.0014 (9) | −0.0022 (9) |
C15 | 0.0229 (12) | 0.0219 (11) | 0.0186 (11) | 0.0024 (9) | −0.0017 (9) | −0.0015 (9) |
C16 | 0.0219 (12) | 0.0192 (11) | 0.0181 (10) | 0.0006 (9) | 0.0010 (8) | 0.0019 (8) |
C17 | 0.0366 (15) | 0.0312 (13) | 0.0211 (12) | −0.0114 (11) | 0.0012 (10) | −0.0017 (10) |
F11 | 0.0778 (13) | 0.0264 (8) | 0.0470 (10) | −0.0049 (8) | 0.0160 (9) | 0.0091 (7) |
F12 | 0.0539 (10) | 0.0476 (9) | 0.0195 (7) | −0.0222 (8) | 0.0094 (7) | −0.0028 (6) |
F13 | 0.0452 (10) | 0.0723 (12) | 0.0357 (9) | −0.0356 (9) | −0.0054 (7) | 0.0116 (9) |
C18 | 0.0311 (13) | 0.0230 (12) | 0.0216 (11) | −0.0030 (10) | −0.0032 (10) | −0.0001 (9) |
F14 | 0.0604 (11) | 0.0470 (9) | 0.0238 (8) | −0.0254 (9) | −0.0111 (7) | 0.0000 (7) |
F15 | 0.0637 (12) | 0.0499 (10) | 0.0263 (8) | 0.0303 (9) | −0.0095 (8) | 0.0010 (7) |
F16 | 0.0377 (9) | 0.0485 (9) | 0.0190 (7) | −0.0039 (7) | 0.0022 (6) | 0.0025 (6) |
C21 | 0.0199 (11) | 0.0199 (10) | 0.0152 (10) | 0.0005 (9) | −0.0008 (8) | −0.0032 (8) |
C22 | 0.0220 (12) | 0.0211 (11) | 0.0207 (11) | 0.0019 (9) | −0.0018 (9) | −0.0014 (9) |
C23 | 0.0192 (11) | 0.0241 (11) | 0.0204 (11) | 0.0000 (9) | 0.0006 (9) | −0.0024 (9) |
C24 | 0.0229 (11) | 0.0212 (11) | 0.0189 (10) | −0.0038 (9) | 0.0010 (9) | −0.0016 (9) |
C25 | 0.0214 (12) | 0.0196 (10) | 0.0175 (10) | −0.0010 (9) | −0.0026 (9) | −0.0011 (8) |
C26 | 0.0173 (11) | 0.0201 (10) | 0.0181 (10) | −0.0005 (9) | −0.0012 (8) | −0.0021 (9) |
C27 | 0.0212 (12) | 0.0304 (13) | 0.0302 (13) | −0.0013 (10) | 0.0019 (10) | 0.0009 (10) |
F21 | 0.0226 (9) | 0.0921 (16) | 0.0765 (14) | 0.0169 (9) | 0.0085 (9) | 0.0476 (12) |
F22 | 0.0235 (9) | 0.0476 (11) | 0.1259 (19) | −0.0106 (8) | 0.0086 (10) | −0.0315 (12) |
F23 | 0.0314 (9) | 0.0826 (13) | 0.0454 (10) | 0.0033 (9) | 0.0150 (8) | −0.0113 (9) |
C28 | 0.0224 (12) | 0.0223 (11) | 0.0234 (11) | −0.0040 (10) | −0.0006 (9) | 0.0022 (9) |
F24 | 0.0352 (8) | 0.0284 (7) | 0.0298 (7) | 0.0013 (6) | 0.0036 (6) | 0.0107 (6) |
F25 | 0.0282 (8) | 0.0286 (8) | 0.0569 (10) | −0.0056 (6) | −0.0192 (7) | 0.0119 (7) |
F26 | 0.0431 (9) | 0.0262 (7) | 0.0306 (8) | 0.0114 (7) | 0.0003 (7) | −0.0012 (6) |
N31 | 0.0316 (18) | 0.044 (2) | 0.045 (2) | 0.000 | 0.000 | 0.0200 (16) |
C32 | 0.033 (2) | 0.040 (2) | 0.047 (2) | 0.000 | 0.000 | 0.0152 (19) |
C33 | 0.071 (4) | 0.041 (3) | 0.090 (4) | 0.000 | 0.000 | 0.024 (3) |
Cu1—N1i | 2.013 (2) | C15—C18 | 1.491 (3) |
Cu1—N1ii | 2.013 (2) | C16—H16 | 0.9500 |
Cu1—N1iii | 2.013 (2) | C17—F12 | 1.334 (3) |
Cu1—N1 | 2.013 (2) | C17—F11 | 1.338 (3) |
Cu1—N31i | 2.499 (3) | C17—F13 | 1.340 (3) |
Cu1—N31 | 2.499 (3) | C18—F16 | 1.330 (3) |
N1—C1 | 1.469 (3) | C18—F14 | 1.332 (3) |
N1—C2 | 1.478 (4) | C18—F15 | 1.355 (3) |
N1—H1 | 0.9300 | C21—C22 | 1.396 (3) |
C1—C1i | 1.546 (6) | C21—C26 | 1.402 (3) |
C1—H1A | 0.9900 | C22—C23 | 1.390 (3) |
C1—H1B | 0.9900 | C22—H22 | 0.9500 |
C2—C3 | 1.529 (4) | C23—C24 | 1.382 (3) |
C2—H2A | 0.9900 | C23—C27 | 1.492 (3) |
C2—H2B | 0.9900 | C24—C25 | 1.386 (3) |
C3—C2iii | 1.529 (4) | C24—H24 | 0.9500 |
C3—H3A | 0.9900 | C25—C26 | 1.390 (3) |
C3—H3B | 0.9900 | C25—C28 | 1.494 (3) |
B1—C21iv | 1.642 (3) | C26—H26 | 0.9500 |
B1—C21 | 1.642 (3) | C27—F22 | 1.317 (3) |
B1—C11iv | 1.644 (3) | C27—F21 | 1.329 (3) |
B1—C11 | 1.644 (3) | C27—F23 | 1.338 (3) |
C11—C16 | 1.399 (3) | C28—F24 | 1.336 (3) |
C11—C12 | 1.404 (3) | C28—F26 | 1.338 (3) |
C12—C13 | 1.380 (3) | C28—F25 | 1.343 (3) |
C12—H12 | 0.9500 | N31—C32 | 1.122 (5) |
C13—C14 | 1.393 (3) | C32—C33 | 1.451 (6) |
C13—C17 | 1.494 (3) | C33—H33A | 0.9800 |
C14—C15 | 1.385 (3) | C33—H33B | 0.9800 |
C14—H14 | 0.9500 | C33—H33C | 0.9800 |
C15—C16 | 1.391 (3) | ||
N1i—Cu1—N1iii | 180.0 | C14—C15—C16 | 121.4 (2) |
N1i—Cu1—N1ii | 93.95 (13) | C14—C15—C18 | 119.3 (2) |
N1iii—Cu1—N1ii | 86.05 (13) | C16—C15—C18 | 119.3 (2) |
N1i—Cu1—N1 | 86.05 (13) | C15—C16—C11 | 121.8 (2) |
N1iii—Cu1—N1 | 93.95 (13) | C15—C16—H16 | 119.1 |
N1ii—Cu1—N1 | 180.0 | C11—C16—H16 | 119.1 |
N1i—Cu1—N31i | 93.56 (9) | F12—C17—F11 | 105.7 (2) |
N1iii—Cu1—N31i | 86.44 (9) | F12—C17—F13 | 106.1 (2) |
N1ii—Cu1—N31i | 93.56 (9) | F11—C17—F13 | 105.8 (2) |
N1—Cu1—N31i | 86.44 (9) | F12—C17—C13 | 112.7 (2) |
N1i—Cu1—N31 | 86.44 (9) | F11—C17—C13 | 113.2 (2) |
N1iii—Cu1—N31 | 93.56 (9) | F13—C17—C13 | 112.7 (2) |
N1ii—Cu1—N31 | 86.44 (9) | F16—C18—F14 | 106.18 (19) |
N1—Cu1—N31 | 93.56 (9) | F16—C18—F15 | 105.12 (19) |
N31i—Cu1—N31 | 180.0 | F14—C18—F15 | 106.3 (2) |
C1—N1—C2 | 111.5 (2) | F16—C18—C15 | 113.6 (2) |
C1—N1—Cu1 | 107.58 (17) | F14—C18—C15 | 113.70 (19) |
C2—N1—Cu1 | 118.07 (19) | F15—C18—C15 | 111.27 (19) |
C1—N1—H1 | 106.3 | C22—C21—C26 | 115.3 (2) |
C2—N1—H1 | 106.3 | C22—C21—B1 | 124.22 (18) |
Cu1—N1—H1 | 106.3 | C26—C21—B1 | 120.25 (18) |
N1—C1—C1i | 107.70 (17) | C23—C22—C21 | 122.5 (2) |
N1—C1—H1A | 110.2 | C23—C22—H22 | 118.7 |
C1i—C1—H1A | 110.2 | C21—C22—H22 | 118.7 |
N1—C1—H1B | 110.2 | C24—C23—C22 | 121.0 (2) |
C1i—C1—H1B | 110.2 | C24—C23—C27 | 118.4 (2) |
H1A—C1—H1B | 108.5 | C22—C23—C27 | 120.6 (2) |
N1—C2—C3 | 111.0 (3) | C23—C24—C25 | 117.8 (2) |
N1—C2—H2A | 109.4 | C23—C24—H24 | 121.1 |
C3—C2—H2A | 109.4 | C25—C24—H24 | 121.1 |
N1—C2—H2B | 109.4 | C24—C25—C26 | 121.0 (2) |
C3—C2—H2B | 109.4 | C24—C25—C28 | 119.3 (2) |
H2A—C2—H2B | 108.0 | C26—C25—C28 | 119.6 (2) |
C2—C3—C2iii | 113.7 (4) | C25—C26—C21 | 122.4 (2) |
C2—C3—H3A | 108.8 | C25—C26—H26 | 118.8 |
C2iii—C3—H3A | 108.8 | C21—C26—H26 | 118.8 |
C2—C3—H3B | 108.8 | F22—C27—F21 | 107.9 (2) |
C2iii—C3—H3B | 108.8 | F22—C27—F23 | 104.9 (2) |
H3A—C3—H3B | 107.7 | F21—C27—F23 | 104.6 (2) |
C21iv—B1—C21 | 106.2 (2) | F22—C27—C23 | 112.7 (2) |
C21iv—B1—C11iv | 113.07 (10) | F21—C27—C23 | 113.3 (2) |
C21—B1—C11iv | 109.45 (11) | F23—C27—C23 | 112.7 (2) |
C21iv—B1—C11 | 109.45 (11) | F24—C28—F26 | 106.47 (17) |
C21—B1—C11 | 113.07 (10) | F24—C28—F25 | 106.18 (18) |
C11iv—B1—C11 | 105.7 (2) | F26—C28—F25 | 105.90 (19) |
C16—C11—C12 | 115.8 (2) | F24—C28—C25 | 113.30 (19) |
C16—C11—B1 | 125.64 (18) | F26—C28—C25 | 111.95 (18) |
C12—C11—B1 | 118.52 (18) | F25—C28—C25 | 112.52 (18) |
C13—C12—C11 | 122.5 (2) | C32—N31—Cu1 | 166.4 (4) |
C13—C12—H12 | 118.8 | N31—C32—C33 | 179.8 (5) |
C11—C12—H12 | 118.8 | C32—C33—H33A | 109.5 |
C12—C13—C14 | 120.8 (2) | C32—C33—H33B | 109.5 |
C12—C13—C17 | 120.3 (2) | H33A—C33—H33B | 109.5 |
C14—C13—C17 | 118.9 (2) | C32—C33—H33C | 109.5 |
C15—C14—C13 | 117.7 (2) | H33A—C33—H33C | 109.5 |
C15—C14—H14 | 121.2 | H33B—C33—H33C | 109.5 |
C13—C14—H14 | 121.2 |
Symmetry codes: (i) x, −y, −z; (ii) −x+1, −y, −z; (iii) −x+1, y, z; (iv) −x+1/2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F15v | 0.93 | 2.25 | 3.055 (3) | 145 |
C22—H22···F21 | 0.95 | 2.39 | 2.733 (3) | 101 |
Symmetry code: (v) x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H3N)2(C10H24N4)](C32H12BF24)2·0.31H2O |
Mr | 2077.43 |
Crystal system, space group | Orthorhombic, Cmca |
Temperature (K) | 120 |
a, b, c (Å) | 25.7320 (6), 18.3516 (4), 17.5412 (4) |
V (Å3) | 8283.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.22 × 0.12 × 0.04 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.920, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32892, 4855, 3525 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.139, 1.02 |
No. of reflections | 4855 |
No. of parameters | 315 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0731P)2 + 12.7378P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.64, −0.37 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS86 (Sheldrick, 1986), SHELXL97 (Sheldrick, 1997), ORTEX in OSCAIL (McArdle, 1994, 2000) and ORTEPIII for Windows (Farrugia, 1997).
Cu1—N1i | 2.013 (2) | Cu1—N1 | 2.013 (2) |
Cu1—N1ii | 2.013 (2) | Cu1—N31i | 2.499 (3) |
Cu1—N1iii | 2.013 (2) | Cu1—N31 | 2.499 (3) |
N1i—Cu1—N1iii | 180.0 | N1ii—Cu1—N31i | 93.56 (9) |
N1i—Cu1—N1ii | 93.95 (13) | N1—Cu1—N31i | 86.44 (9) |
N1iii—Cu1—N1ii | 86.05 (13) | N1i—Cu1—N31 | 86.44 (9) |
N1i—Cu1—N1 | 86.05 (13) | N1iii—Cu1—N31 | 93.56 (9) |
N1iii—Cu1—N1 | 93.95 (13) | N1ii—Cu1—N31 | 86.44 (9) |
N1ii—Cu1—N1 | 180.0 | N1—Cu1—N31 | 93.56 (9) |
N1i—Cu1—N31i | 93.56 (9) | N31i—Cu1—N31 | 180.0 |
N1iii—Cu1—N31i | 86.44 (9) |
Symmetry codes: (i) x, −y, −z; (ii) −x+1, −y, −z; (iii) −x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F15iv | 0.93 | 2.25 | 3.055 (3) | 144.7 |
C22—H22···F21 | 0.95 | 2.39 | 2.733 (3) | 100.6 |
Symmetry code: (iv) x, y−1/2, −z+1/2. |
1,4,8,11-Tetraazacyclotetradecane (cyclam) and its derivatives have been studied extensively as ligands for transition metal complexes, including copper compounds. Among the copper(II)–cyclam complexes whose crystal structures have been reported are neutral complexes, such as [CuII(cyclam)(SC6F5)2], (I) [Cambridge Structural Database (Allen, 2002) refcode BUTYUK; Addison & Sinn, 1983], [CuII(cyclam)Br2], (II) (TEGPOK; Chen et al., 1996; see also Matsuo et al., 2001), and [CuII(cyclam)(ClO4)2], (III) (PTZDCU; Taskar & Sklar, 1975), and ionic complexes, for example [CuII(cyclam)(H2O)2][F(H2O)4]2, (IV) (JABSUA10; Emsley et al., 1990; see also Matsuo et al., 2001), [CuII(cyclam)][CuIBr3], (V) (QIWVAT; Willett & Vij, 2000), [CuIICl(cyclam)]2[CdCl4], (VI) (YUMBUD; Pickardt & Hoffmeister, 1995), [CuII(cyclam)][CdCl3(H2O)2]Cl, (VII) (YUMCAK; Pickardt & Hoffmeister, 1995), [CuII(NCS)(cyclam)][SCN], (VIII) (ZUZJUZ; Lu et al., 1996) and [CuII(cyclam)][BH4]2, (IX) (HAFSUC; Antsyshkina et al., 1992). In complexes (I)–(VII), copper is six-coordinated, with the four N atoms of the cyclam ligand in the equatorial sites of a distorted octahedral structures. The axial ligands in (I)–(IV) are the other bound ligands [SC6F5 in (I), Br in (II), OClO3 in (III) and OH2 in (IV)], while in (V)–(VII), the axial sites are occupied by halides, including bridging ligands from the halometallete anions. In contrast to the situation in (I)–(VII), the Cu centre in (VIII) has essentially a distorted square-pyramidal geometry, with the bound isothiocyanate ligand in the axial site; however, there is also a weak Cu···S interaction with a neighbouring cation, at a distance only ca 0.185 Å less than the sum of the van der Waals radii.
In order to study the effect of a large non-interacting anion on the structure of a copper(II)–cyclam complex, a complex with the [B{C6H3(CF3)2-3,5}4] anion was sought. The title compound, (X), was obtained on recrystallizing the reaction product from cyclam, Cu(ClO4)2·6H2O and Na[B{C6H3(CF3)2-3,5}4] from MeCN/Et2O solution.
Complex (X), in space group Cmca, exists as an ionic species with no interactions between the distorted octahedral [CuII(cyclam)(NCMe)2]2+ dications (Figs. 1a and 1 b) and the distorted tetrahedral [B{C6H3(CF3)-3,5}4]-1 anions (Fig. 1c). The arrangement of these molecules in the unit cell is shown in Fig. 2. As in complexes (I)–(VII), the equatorial sites in the dication of (X) are occupied by the four cyclam N atoms; the uniform Cu—Ncyclam bond length is 2.013 (2) Å and is within the range found in the other Cu(cyclam) complexes. The axial Cu—Nacetonitrile bond lengths are much longer [2.499 (4) Å]. The distortion from an ideal octahedral geometry is small, as shown by the N—Cu—N bond angles (Table 1). The equatorial N—Cu—N angles [N1—Cu1—N1i and N1ii—Cu1—N1iii] within the five-membered rings are, as expected, smaller than those within the six-membered rings [N1—Cu1—N1iii and N1i—Cu1—N1ii], viz. 86.05 (9) versus 93.95 (9)°, respectively. The Naxial—Cu—Nequatorial angles are 93.55 (9) and 86.45 (9)°, with an Naxial—Cu—Naxial angle of 180°. The Cu—N≡C(Me) fragment is nearly linear [Cu1—N31—C32 = 166.3 (3)°], and the terminal methyl group is disordered. The configurations of the four chiral N centres in (X) are 1RS, 4RS, 8SR and 11SR. On th basis off the puckering parameters of Cremer & Pople (1975), the six-membered chelate rings have near chair-shaped conformations [Q = 0.591 (4) Å, θ = 12.6 (3)° and φ = 180.0 (14)°], while the five-membered rings have twist conformations [Q = 0.454 (3) Å and φ = 270.0 (3)°].
The C—B—C bond angles in the anion of (X) are clustered around the ideal tetrahedral angle of 109.5°, being between 105.7 (2) and 113.04 (11)°.
Water molecules are disordered between columns of anions, which form parallel to (011) (Figure 2c), with approximately one-third of a water atom present in the formula unit.