The pendent-arm macrocyclic hexaamine trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L) may coordinate in tetra-, penta- or hexadentate modes, depending on the metal ion and the synthetic procedure. We report here the crystal structures of two pseudo-octahedral cobalt(III) complexes of L, namely sodium trans-cyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine)cobalt(III) triperchlorate, Na[Co(CN)(C13H30N6)](ClO4)3 or Na{trans-[CoL(CN)]}(ClO4)3, (I), where L is coordinated as a pentadentate ligand, and trans-dicyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine)cobalt(III) trans-dicyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diaminium)cobalt(III) tetraperchlorate tetrahydrate, [Co(CN)2(C14H32N6)][Co(CN)2(C14H30N6)](ClO4)4·4H2O or trans-[CoL(CN)2]trans-[Co(H2L)(CN)2](ClO4)4·4H2O, (II), where the ligand binds in a tetradentate mode, with the remaining coordination sites being filled by C-bound cyano ligands. In (I), the secondary amine Co-N bond lengths lie within the range 1.944 (3)-1.969 (3) Å, while the trans influence of the cyano ligand lengthens the Co-N bond length of the coordinated primary amine [Co-N = 1.986 (3) Å]. The Co-CN bond length is 1.899 (3) Å. The complex cations in (II) are each located on centres of symmetry. The Co-N bond lengths in both cations are somewhat longer than in (I) and span a narrow range [1.972 (3)-1.982 (3) Å]. The two independent Co-CN bond lengths are similar [1.918 (4) and 1.926 (4) Å] but significantly longer than in the structure of (I), again a consequence of the trans influence of each cyano ligand.
Supporting information
CCDC references: 273029; 273030
In a well ventilated fume hood, a solution of CoCl2·6H2O (0.23 g) and L.6 HCl (0.5 g) in water (40 ml) was prepared and immediately the pH was raised to 6 with dilute NaOH to give a red solution. After stirring for 2 min, NaCN (0.15 g; Caution! Extremely toxic) was added and the mixture was stirred at 333 K for 1 h, whereupon the colour of the solution turned to yellow. The mixture was diluted to 200 ml and charged on a column of Sephadex C25 cation-exchange resin (10 cm × 2 cm). Three well separated yellow bands eluted in the order trans-[CoL(CN)2]+ (0.1 M NaClO4), trans-[CoL(CN)]2+ (0.2 M NaClO4) and [CoL]3+ (0.5 M NaClO4). The compound trans-[CoL(CN)2]trans-[Co(H2L)(CN)2](ClO4)4·4H2O crystallized from the first band after concentration to ca 20 ml and acidification to pH 3. Na{trans-[CoL(CN)]}(ClO4)3 crystallized from a concentrated solution of band 2 at pH 7. These crystals were filtered off and air dried. The complex from the third band, [CoL](ClO4)3, has been described previously (Bernhardt et al., 1989).
Water H atoms were identified from difference maps and their positional and thermal parameters were restrained during subsequent refinement cycles, with O—H = 0.89 (1) Å and with Uiso(H) = 1.5Ueq(O). Please check added text. The H atoms of the pendent amines and ammonio groups in both structures were first identified from difference maps and then constrained, with N—H = 0.89 Å and with Uiso(H) = 1.5Ueq(N). Please check added text. All alkyl H atoms were treated as riding, with C—H distances ranging from 0.93 to 0.97 Å and with Uiso(H) = 1.5 (methyl H atoms) or 1.2 (all other atoms) Ueq(C).
Perchlorate disorder was apparent in both structures. In (I), the O atoms O2B, O2C and O2D were refined in two positions with complementary occupancies and with the aid of tetrahedral restraints. In (II), both perchlorate anions were disordered. All O atoms attached to atom Cl1 were identified in two positions and refined with complementary occupancies. In the second anion, a pseudo-mirror plane passing through atoms O2A, O2B and O2C resulted in two different positions for the Cl atom and the remaining O atom. Again, tetrahedral restraints were included. All minor components of the disorder were refined with isotropic displacement parameters.
For both compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
(I) Sodium
trans-cyano(
trans-6,13-dimethyl-,1,4,8,11-tetraazacyclotetradecane- 6,13-diamine)cobalt triperchlorate
top
Crystal data top
Na[Co(C13H30N7)](ClO4)3 | Z = 2 |
Mr = 664.71 | F(000) = 684 |
Triclinic, P1 | Dx = 1.706 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.405 (2) Å | Cell parameters from 25 reflections |
b = 10.683 (2) Å | θ = 11.3–14.1° |
c = 14.211 (2) Å | µ = 1.06 mm−1 |
α = 94.02 (1)° | T = 294 K |
β = 100.62 (2)° | Prism, yellow |
γ = 111.21 (1)° | 0.27 × 0.27 × 0.07 mm |
V = 1293.7 (4) Å3 | |
Data collection top
Enraf-Nonius TurboCAD4 diffractometer | 3275 reflections with I > 2σ(I) |
Radiation source: Enraf-Nonius FR590 | Rint = 0.018 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
non–profiled ω/2θ scans | h = 0→11 |
Absorption correction: ψ scan (North et al., 1968) Number of ψ scan sets used was 4
Theta correction was applied. Averaged transmission function
was used. No Fourier smoothing was applied. | k = −12→11 |
Tmin = 0.799, Tmax = 0.928 | l = −16→16 |
4846 measured reflections | 3 standard reflections every 120 min |
4546 independent reflections | intensity decay: 7% |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0576P)2 + 1.1231P] where P = (Fo2 + 2Fc2)/3 |
4546 reflections | (Δ/σ)max = 0.001 |
348 parameters | Δρmax = 0.50 e Å−3 |
9 restraints | Δρmin = −0.43 e Å−3 |
Crystal data top
Na[Co(C13H30N7)](ClO4)3 | γ = 111.21 (1)° |
Mr = 664.71 | V = 1293.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.405 (2) Å | Mo Kα radiation |
b = 10.683 (2) Å | µ = 1.06 mm−1 |
c = 14.211 (2) Å | T = 294 K |
α = 94.02 (1)° | 0.27 × 0.27 × 0.07 mm |
β = 100.62 (2)° | |
Data collection top
Enraf-Nonius TurboCAD4 diffractometer | 3275 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) Number of ψ scan sets used was 4
Theta correction was applied. Averaged transmission function
was used. No Fourier smoothing was applied. | Rint = 0.018 |
Tmin = 0.799, Tmax = 0.928 | 3 standard reflections every 120 min |
4846 measured reflections | intensity decay: 7% |
4546 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 9 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.50 e Å−3 |
4546 reflections | Δρmin = −0.43 e Å−3 |
348 parameters | |
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 | Occ. (<1) |
C1 | 0.0261 (4) | 0.4358 (4) | 0.8374 (3) | 0.0372 (8) | |
H1A | −0.0610 | 0.3950 | 0.8676 | 0.045* | |
H1B | −0.0095 | 0.4746 | 0.7825 | 0.045* | |
C2 | 0.1596 (5) | 0.5449 (4) | 0.9093 (3) | 0.0406 (9) | |
H2A | 0.1324 | 0.6225 | 0.9231 | 0.049* | |
H2B | 0.1816 | 0.5105 | 0.9694 | 0.049* | |
C3 | 0.3107 (5) | 0.6902 (4) | 0.8006 (3) | 0.0451 (10) | |
H3A | 0.3897 | 0.7769 | 0.8334 | 0.054* | |
H3B | 0.2112 | 0.7007 | 0.7838 | 0.054* | |
C4 | 0.3542 (4) | 0.6472 (4) | 0.7091 (3) | 0.0414 (9) | |
C5 | 0.5146 (5) | 0.6378 (4) | 0.7269 (3) | 0.0501 (11) | |
H5A | 0.5386 | 0.6173 | 0.6656 | 0.060* | |
H5B | 0.5940 | 0.7241 | 0.7599 | 0.060* | |
C6 | 0.5813 (5) | 0.4327 (5) | 0.7518 (3) | 0.0499 (11) | |
H6A | 0.6204 | 0.3938 | 0.8054 | 0.060* | |
H6B | 0.6677 | 0.4800 | 0.7227 | 0.060* | |
C7 | 0.4549 (5) | 0.3227 (4) | 0.6782 (3) | 0.0474 (10) | |
H7A | 0.4291 | 0.3589 | 0.6196 | 0.057* | |
H7B | 0.4903 | 0.2509 | 0.6620 | 0.057* | |
C8 | 0.1729 (5) | 0.1750 (4) | 0.6480 (2) | 0.0398 (9) | |
H8A | 0.1937 | 0.0981 | 0.6229 | 0.048* | |
H8B | 0.1538 | 0.2224 | 0.5943 | 0.048* | |
C9 | 0.0261 (5) | 0.1226 (3) | 0.6879 (3) | 0.0380 (9) | |
C10 | −0.0259 (4) | 0.2351 (4) | 0.7191 (3) | 0.0364 (8) | |
H10A | −0.0365 | 0.2851 | 0.6656 | 0.044* | |
H10B | −0.1281 | 0.1947 | 0.7339 | 0.044* | |
C11 | 0.3419 (5) | 0.7380 (4) | 0.6321 (3) | 0.0594 (13) | |
H11A | 0.3600 | 0.7024 | 0.5736 | 0.089* | |
H11B | 0.4187 | 0.8282 | 0.6548 | 0.089* | |
H11C | 0.2392 | 0.7405 | 0.6195 | 0.089* | |
C12 | −0.1075 (6) | 0.0239 (4) | 0.6053 (3) | 0.0591 (13) | |
H12A | −0.0795 | −0.0495 | 0.5840 | 0.089* | |
H12B | −0.1240 | 0.0716 | 0.5521 | 0.089* | |
H12C | −0.2019 | −0.0116 | 0.6284 | 0.089* | |
C13 | 0.3701 (4) | 0.3654 (3) | 0.9114 (2) | 0.0289 (7) | |
Co1 | 0.30057 (5) | 0.42401 (4) | 0.79490 (3) | 0.02666 (14) | |
N1 | 0.0846 (3) | 0.3312 (3) | 0.80485 (19) | 0.0294 (6) | |
H1 | 0.0879 | 0.2812 | 0.8539 | 0.035* | |
N2 | 0.2990 (3) | 0.5854 (3) | 0.8661 (2) | 0.0348 (7) | |
H2 | 0.3857 | 0.6187 | 0.9154 | 0.042* | |
N3 | 0.5154 (3) | 0.5292 (3) | 0.7871 (2) | 0.0391 (7) | |
H3 | 0.5718 | 0.5697 | 0.8480 | 0.047* | |
N4 | 0.3137 (4) | 0.2677 (3) | 0.7204 (2) | 0.0345 (7) | |
H4 | 0.3364 | 0.2161 | 0.7646 | 0.041* | |
N5 | 0.2435 (3) | 0.5032 (3) | 0.6783 (2) | 0.0334 (7) | |
H5C | 0.2607 | 0.4652 | 0.6252 | 0.040* | |
H5D | 0.1430 | 0.4953 | 0.6673 | 0.040* | |
N6 | 0.0594 (4) | 0.0564 (3) | 0.7720 (2) | 0.0456 (8) | |
H6C | 0.0587 | −0.0203 | 0.7410 | 0.055* | |
H6D | −0.0341 | 0.0305 | 0.7881 | 0.055* | |
N7 | 0.4075 (4) | 0.3263 (3) | 0.9799 (2) | 0.0380 (7) | |
Cl1 | 0.06564 (11) | 0.21045 (9) | 1.07064 (6) | 0.0378 (2) | |
O1A | 0.1344 (4) | 0.3540 (3) | 1.0947 (2) | 0.0579 (8) | |
O1B | 0.1742 (4) | 0.1535 (3) | 1.1136 (3) | 0.0676 (9) | |
O1C | 0.0306 (4) | 0.1714 (3) | 0.9680 (2) | 0.0693 (10) | |
O1D | −0.0754 (3) | 0.1573 (3) | 1.1047 (2) | 0.0480 (7) | |
Cl2 | 0.42260 (12) | −0.08820 (10) | 1.13885 (8) | 0.0504 (3) | |
O2A | 0.5859 (3) | −0.0639 (3) | 1.1619 (3) | 0.0636 (9) | |
O2B | 0.3985 (6) | 0.0127 (4) | 1.0913 (6) | 0.111 (3) | 0.882 (10) |
O2C | 0.3820 (8) | −0.0714 (11) | 1.2271 (5) | 0.178 (4) | 0.882 (10) |
O2D | 0.3287 (6) | −0.2170 (4) | 1.0927 (6) | 0.125 (3) | 0.882 (10) |
O2E | 0.347 (3) | −0.193 (2) | 1.1852 (19) | 0.059 (10)* | 0.118 (10) |
O2F | 0.382 (3) | −0.132 (3) | 1.0396 (11) | 0.081 (13)* | 0.118 (10) |
O2G | 0.385 (3) | 0.0217 (17) | 1.159 (2) | 0.057 (9)* | 0.118 (10) |
Cl3 | 0.13169 (13) | 0.38346 (12) | 0.41303 (7) | 0.0524 (3) | |
O3A | 0.0347 (5) | 0.3161 (5) | 0.4738 (3) | 0.1048 (16) | |
O3B | 0.1142 (7) | 0.2987 (5) | 0.3281 (3) | 0.1223 (18) | |
O3C | 0.0928 (5) | 0.4920 (4) | 0.3846 (3) | 0.0978 (14) | |
O3D | 0.2896 (4) | 0.4333 (5) | 0.4667 (3) | 0.0886 (12) | |
Na1 | 0.2567 (2) | 0.06782 (16) | 0.95955 (13) | 0.0556 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.036 (2) | 0.039 (2) | 0.042 (2) | 0.0213 (17) | 0.0086 (16) | 0.0054 (16) |
C2 | 0.054 (2) | 0.035 (2) | 0.038 (2) | 0.0251 (19) | 0.0077 (18) | −0.0002 (16) |
C3 | 0.049 (2) | 0.0236 (18) | 0.055 (2) | 0.0095 (17) | −0.0012 (19) | 0.0079 (17) |
C4 | 0.036 (2) | 0.0258 (18) | 0.050 (2) | 0.0005 (16) | −0.0018 (17) | 0.0166 (16) |
C5 | 0.036 (2) | 0.045 (2) | 0.058 (3) | 0.0029 (18) | 0.0037 (19) | 0.021 (2) |
C6 | 0.034 (2) | 0.067 (3) | 0.054 (2) | 0.020 (2) | 0.0139 (19) | 0.021 (2) |
C7 | 0.049 (3) | 0.061 (3) | 0.046 (2) | 0.030 (2) | 0.023 (2) | 0.015 (2) |
C8 | 0.055 (2) | 0.034 (2) | 0.0262 (18) | 0.0156 (18) | 0.0033 (17) | −0.0004 (15) |
C9 | 0.047 (2) | 0.0284 (18) | 0.0269 (18) | 0.0072 (17) | −0.0040 (16) | 0.0002 (14) |
C10 | 0.031 (2) | 0.0318 (19) | 0.0355 (19) | 0.0031 (16) | −0.0003 (15) | 0.0024 (15) |
C11 | 0.057 (3) | 0.045 (2) | 0.064 (3) | 0.008 (2) | 0.000 (2) | 0.030 (2) |
C12 | 0.065 (3) | 0.040 (2) | 0.044 (2) | −0.001 (2) | −0.005 (2) | −0.0077 (19) |
C13 | 0.0291 (18) | 0.0234 (16) | 0.0295 (18) | 0.0079 (14) | 0.0012 (14) | 0.0003 (14) |
Co1 | 0.0276 (3) | 0.0244 (2) | 0.0251 (2) | 0.00892 (19) | 0.00044 (18) | 0.00501 (17) |
N1 | 0.0332 (16) | 0.0274 (14) | 0.0258 (14) | 0.0096 (13) | 0.0060 (12) | 0.0041 (11) |
N2 | 0.0365 (17) | 0.0252 (15) | 0.0360 (16) | 0.0115 (13) | −0.0058 (13) | 0.0015 (12) |
N3 | 0.0295 (16) | 0.0416 (18) | 0.0402 (17) | 0.0085 (14) | 0.0018 (14) | 0.0123 (14) |
N4 | 0.0416 (18) | 0.0388 (16) | 0.0283 (15) | 0.0205 (14) | 0.0084 (13) | 0.0085 (13) |
N5 | 0.0313 (16) | 0.0307 (15) | 0.0326 (16) | 0.0077 (13) | 0.0006 (13) | 0.0092 (12) |
N6 | 0.061 (2) | 0.0344 (17) | 0.0389 (18) | 0.0156 (16) | 0.0098 (16) | 0.0074 (14) |
N7 | 0.0408 (18) | 0.0325 (16) | 0.0350 (17) | 0.0107 (14) | 0.0003 (14) | 0.0088 (13) |
Cl1 | 0.0426 (5) | 0.0325 (5) | 0.0381 (5) | 0.0137 (4) | 0.0100 (4) | 0.0054 (4) |
O1A | 0.0582 (19) | 0.0328 (15) | 0.079 (2) | 0.0103 (14) | 0.0225 (16) | 0.0027 (14) |
O1B | 0.062 (2) | 0.065 (2) | 0.088 (2) | 0.0372 (18) | 0.0140 (18) | 0.0259 (18) |
O1C | 0.075 (2) | 0.074 (2) | 0.0351 (16) | 0.0018 (18) | 0.0132 (15) | 0.0028 (15) |
O1D | 0.0463 (17) | 0.0457 (16) | 0.0563 (17) | 0.0165 (13) | 0.0223 (14) | 0.0134 (13) |
Cl2 | 0.0374 (5) | 0.0383 (5) | 0.0742 (7) | 0.0141 (4) | 0.0085 (5) | 0.0128 (5) |
O2A | 0.0432 (18) | 0.061 (2) | 0.085 (2) | 0.0237 (16) | 0.0033 (16) | 0.0108 (17) |
O2B | 0.075 (3) | 0.057 (3) | 0.172 (7) | 0.019 (2) | −0.036 (4) | 0.037 (3) |
O2C | 0.093 (5) | 0.288 (12) | 0.116 (5) | 0.020 (5) | 0.056 (4) | −0.016 (6) |
O2D | 0.069 (3) | 0.036 (2) | 0.225 (8) | 0.012 (2) | −0.041 (4) | −0.020 (3) |
Cl3 | 0.0597 (7) | 0.0731 (7) | 0.0332 (5) | 0.0346 (6) | 0.0088 (5) | 0.0176 (5) |
O3A | 0.077 (3) | 0.173 (5) | 0.081 (3) | 0.049 (3) | 0.031 (2) | 0.080 (3) |
O3B | 0.161 (5) | 0.103 (3) | 0.079 (3) | 0.029 (3) | 0.031 (3) | −0.025 (3) |
O3C | 0.093 (3) | 0.102 (3) | 0.115 (3) | 0.058 (3) | 0.009 (3) | 0.049 (3) |
O3D | 0.060 (2) | 0.141 (4) | 0.065 (2) | 0.044 (2) | 0.0022 (18) | 0.023 (2) |
Na1 | 0.0573 (11) | 0.0376 (9) | 0.0672 (11) | 0.0126 (8) | 0.0160 (9) | 0.0021 (8) |
Geometric parameters (Å, º) top
C1—N1 | 1.494 (4) | Co1—N2 | 1.944 (3) |
C1—C2 | 1.509 (5) | Co1—N3 | 1.953 (3) |
C1—H1A | 0.9700 | Co1—N4 | 1.969 (3) |
C1—H1B | 0.9700 | Co1—N5 | 1.986 (3) |
C2—N2 | 1.485 (5) | C13—Co1 | 1.899 (3) |
C2—H2A | 0.9700 | N1—H1 | 0.9100 |
C2—H2B | 0.9700 | N2—H2 | 0.9100 |
C3—N2 | 1.492 (4) | N3—H3 | 0.9100 |
C3—C4 | 1.523 (6) | N4—H4 | 0.9100 |
C3—H3A | 0.9700 | N5—H5C | 0.9000 |
C3—H3B | 0.9700 | N5—H5D | 0.9000 |
C4—N5 | 1.490 (4) | N6—Na1 | 2.920 (4) |
C4—C5 | 1.524 (6) | N6—H6C | 0.9000 |
C4—C11 | 1.528 (5) | N6—H6D | 0.9000 |
C5—N3 | 1.490 (5) | N7—Na1 | 2.574 (3) |
C5—H5A | 0.9700 | Cl1—O1A | 1.419 (3) |
C5—H5B | 0.9700 | Cl1—O1D | 1.430 (3) |
C6—N3 | 1.485 (5) | Cl1—O1C | 1.431 (3) |
C6—C7 | 1.499 (6) | Cl1—O1B | 1.434 (3) |
C6—H6A | 0.9700 | Cl1—Na1 | 3.276 (2) |
C6—H6B | 0.9700 | Cl1—Na1i | 3.321 (2) |
C7—N4 | 1.498 (5) | O1B—Na1 | 2.663 (4) |
C7—H7A | 0.9700 | O1C—Na1 | 2.746 (4) |
C7—H7B | 0.9700 | O1D—Na1i | 2.383 (3) |
C8—N4 | 1.483 (5) | Cl2—O2G | 1.368 (14) |
C8—C9 | 1.523 (6) | Cl2—O2D | 1.372 (4) |
C8—H8A | 0.9700 | Cl2—O2B | 1.375 (4) |
C8—H8B | 0.9700 | Cl2—O2E | 1.377 (14) |
C9—N6 | 1.472 (5) | Cl2—O2F | 1.390 (14) |
C9—C10 | 1.520 (5) | Cl2—O2C | 1.394 (6) |
C9—C12 | 1.547 (5) | Cl2—O2A | 1.431 (3) |
C10—N1 | 1.485 (4) | O2A—Na1ii | 2.480 (4) |
C10—H10A | 0.9700 | O2B—Na1 | 2.331 (5) |
C10—H10B | 0.9700 | O2F—Na1 | 2.99 (3) |
C11—H11A | 0.9600 | O2G—Na1 | 3.01 (3) |
C11—H11B | 0.9600 | Cl3—O3C | 1.399 (4) |
C11—H11C | 0.9600 | Cl3—O3B | 1.404 (4) |
C12—H12A | 0.9600 | Cl3—O3A | 1.414 (4) |
C12—H12B | 0.9600 | Cl3—O3D | 1.423 (4) |
C12—H12C | 0.9600 | Na1—O1Di | 2.383 (3) |
C13—N7 | 1.132 (4) | Na1—O2Aii | 2.480 (4) |
Co1—N1 | 1.949 (3) | Na1—Cl1i | 3.321 (2) |
| | | |
N1—C1—C2 | 107.7 (3) | C4—N5—H5D | 111.8 |
N1—C1—H1A | 110.2 | Co1—N5—H5D | 111.8 |
C2—C1—H1A | 110.2 | H5C—N5—H5D | 109.5 |
N1—C1—H1B | 110.2 | C9—N6—Na1 | 149.4 (2) |
C2—C1—H1B | 110.2 | C9—N6—H6C | 99.3 |
H1A—C1—H1B | 108.5 | Na1—N6—H6C | 99.3 |
N2—C2—C1 | 107.9 (3) | C9—N6—H6D | 99.3 |
N2—C2—H2A | 110.1 | Na1—N6—H6D | 99.3 |
C1—C2—H2A | 110.1 | H6C—N6—H6D | 104.0 |
N2—C2—H2B | 110.1 | C13—N7—Na1 | 109.3 (2) |
C1—C2—H2B | 110.1 | O1A—Cl1—O1D | 110.40 (18) |
H2A—C2—H2B | 108.4 | O1A—Cl1—O1C | 110.4 (2) |
N2—C3—C4 | 109.6 (3) | O1D—Cl1—O1C | 109.12 (19) |
N2—C3—H3A | 109.7 | O1A—Cl1—O1B | 109.4 (2) |
C4—C3—H3A | 109.7 | O1D—Cl1—O1B | 109.75 (19) |
N2—C3—H3B | 109.7 | O1C—Cl1—O1B | 107.7 (2) |
C4—C3—H3B | 109.7 | O1A—Cl1—Na1 | 116.46 (14) |
H3A—C3—H3B | 108.2 | O1D—Cl1—Na1 | 133.10 (13) |
N5—C4—C3 | 103.6 (3) | O1C—Cl1—Na1 | 56.03 (17) |
N5—C4—C5 | 103.5 (3) | O1B—Cl1—Na1 | 52.66 (15) |
C3—C4—C5 | 113.9 (3) | O1A—Cl1—Na1i | 146.49 (14) |
N5—C4—C11 | 113.3 (3) | O1D—Cl1—Na1i | 38.84 (12) |
C3—C4—C11 | 112.1 (3) | O1C—Cl1—Na1i | 79.15 (14) |
C5—C4—C11 | 110.1 (3) | O1B—Cl1—Na1i | 97.07 (15) |
N3—C5—C4 | 109.8 (3) | Na1—Cl1—Na1i | 95.76 (5) |
N3—C5—H5A | 109.7 | Cl1—O1B—Na1 | 101.98 (18) |
C4—C5—H5A | 109.7 | Cl1—O1C—Na1 | 98.36 (19) |
N3—C5—H5B | 109.7 | Cl1—O1D—Na1i | 119.05 (17) |
C4—C5—H5B | 109.7 | O2G—Cl2—O2D | 129.9 (11) |
H5A—C5—H5B | 108.2 | O2G—Cl2—O2B | 42.3 (11) |
N3—C6—C7 | 108.7 (3) | O2D—Cl2—O2B | 113.8 (3) |
N3—C6—H6A | 110.0 | O2G—Cl2—O2E | 110.9 (11) |
C7—C6—H6A | 110.0 | O2D—Cl2—O2E | 55.9 (11) |
N3—C6—H6B | 110.0 | O2B—Cl2—O2E | 140.9 (10) |
C7—C6—H6B | 110.0 | O2G—Cl2—O2F | 110.2 (12) |
H6A—C6—H6B | 108.3 | O2D—Cl2—O2F | 53.6 (12) |
N4—C7—C6 | 108.4 (3) | O2B—Cl2—O2F | 71.0 (12) |
N4—C7—H7A | 110.0 | O2E—Cl2—O2F | 109.4 (12) |
C6—C7—H7A | 110.0 | O2G—Cl2—O2C | 62.6 (11) |
N4—C7—H7B | 110.0 | O2D—Cl2—O2C | 107.5 (5) |
C6—C7—H7B | 110.0 | O2B—Cl2—O2C | 104.7 (5) |
H7A—C7—H7B | 108.4 | O2E—Cl2—O2C | 55.4 (11) |
N4—C8—C9 | 113.8 (3) | O2F—Cl2—O2C | 151.2 (10) |
N4—C8—H8A | 108.8 | O2G—Cl2—O2A | 115.9 (10) |
C9—C8—H8A | 108.8 | O2D—Cl2—O2A | 114.0 (3) |
N4—C8—H8B | 108.8 | O2B—Cl2—O2A | 110.1 (3) |
C9—C8—H8B | 108.8 | O2E—Cl2—O2A | 108.0 (9) |
H8A—C8—H8B | 107.7 | O2F—Cl2—O2A | 102.0 (10) |
N6—C9—C10 | 109.1 (3) | O2C—Cl2—O2A | 106.0 (3) |
N6—C9—C8 | 108.1 (3) | Cl2—O2A—Na1ii | 124.6 (2) |
C10—C9—C8 | 112.6 (3) | Cl2—O2B—Na1 | 147.2 (3) |
N6—C9—C12 | 112.7 (3) | Cl2—O2F—Na1 | 103.0 (13) |
C10—C9—C12 | 106.9 (3) | Cl2—O2G—Na1 | 102.4 (13) |
C8—C9—C12 | 107.4 (3) | O3C—Cl3—O3B | 107.0 (3) |
N1—C10—C9 | 113.1 (3) | O3C—Cl3—O3A | 109.5 (3) |
N1—C10—H10A | 109.0 | O3B—Cl3—O3A | 112.7 (3) |
C9—C10—H10A | 109.0 | O3C—Cl3—O3D | 109.7 (3) |
N1—C10—H10B | 109.0 | O3B—Cl3—O3D | 110.0 (3) |
C9—C10—H10B | 109.0 | O3A—Cl3—O3D | 107.9 (2) |
H10A—C10—H10B | 107.8 | O2B—Na1—O1Di | 97.01 (15) |
C4—C11—H11A | 109.5 | O2B—Na1—O2Aii | 100.5 (2) |
C4—C11—H11B | 109.5 | O1Di—Na1—O2Aii | 91.68 (12) |
H11A—C11—H11B | 109.5 | O2B—Na1—N7 | 100.91 (15) |
C4—C11—H11C | 109.5 | O1Di—Na1—N7 | 162.00 (13) |
H11A—C11—H11C | 109.5 | O2Aii—Na1—N7 | 83.40 (12) |
H11B—C11—H11C | 109.5 | O2B—Na1—O1B | 74.9 (2) |
C9—C12—H12A | 109.5 | O1Di—Na1—O1B | 108.39 (12) |
C9—C12—H12B | 109.5 | O2Aii—Na1—O1B | 159.72 (13) |
H12A—C12—H12B | 109.5 | N7—Na1—O1B | 78.27 (11) |
C9—C12—H12C | 109.5 | O2B—Na1—O1C | 125.2 (2) |
H12A—C12—H12C | 109.5 | O1Di—Na1—O1C | 94.76 (12) |
H12B—C12—H12C | 109.5 | O2Aii—Na1—O1C | 132.52 (12) |
N7—C13—Co1 | 177.7 (3) | N7—Na1—O1C | 76.34 (11) |
C13—Co1—N2 | 91.53 (13) | O1B—Na1—O1C | 50.64 (10) |
C13—Co1—N1 | 89.61 (13) | O2B—Na1—N6 | 163.53 (18) |
N2—Co1—N1 | 87.59 (12) | O1Di—Na1—N6 | 68.13 (10) |
C13—Co1—N3 | 91.74 (14) | O2Aii—Na1—N6 | 73.89 (11) |
N2—Co1—N3 | 88.52 (14) | N7—Na1—N6 | 93.88 (11) |
N1—Co1—N3 | 175.91 (13) | O1B—Na1—N6 | 115.68 (12) |
C13—Co1—N4 | 89.49 (13) | O1C—Na1—N6 | 65.35 (10) |
N2—Co1—N4 | 176.49 (13) | O2B—Na1—O2F | 32.3 (3) |
N1—Co1—N4 | 95.77 (12) | O1Di—Na1—O2F | 70.2 (5) |
N3—Co1—N4 | 88.10 (13) | O2Aii—Na1—O2F | 83.5 (4) |
C13—Co1—N5 | 174.43 (13) | N7—Na1—O2F | 126.0 (5) |
N2—Co1—N5 | 84.55 (12) | O1B—Na1—O2F | 100.3 (3) |
N1—Co1—N5 | 94.18 (12) | O1C—Na1—O2F | 142.5 (4) |
N3—Co1—N5 | 84.21 (12) | N6—Na1—O2F | 131.4 (4) |
N4—Co1—N5 | 94.20 (12) | O2B—Na1—O2G | 15.6 (4) |
C10—N1—C1 | 112.0 (3) | O1Di—Na1—O2G | 99.4 (4) |
C10—N1—Co1 | 117.2 (2) | O2Aii—Na1—O2G | 115.6 (4) |
C1—N1—Co1 | 108.2 (2) | N7—Na1—O2G | 98.3 (4) |
C10—N1—H1 | 106.2 | O1B—Na1—O2G | 59.4 (4) |
C1—N1—H1 | 106.2 | O1C—Na1—O2G | 109.6 (4) |
Co1—N1—H1 | 106.2 | N6—Na1—O2G | 165.2 (5) |
C2—N2—C3 | 115.9 (3) | O2F—Na1—O2G | 44.3 (5) |
C2—N2—Co1 | 108.4 (2) | O2B—Na1—Cl1 | 100.2 (2) |
C3—N2—Co1 | 108.8 (2) | O1Di—Na1—Cl1 | 105.67 (9) |
C2—N2—H2 | 107.8 | O2Aii—Na1—Cl1 | 151.01 (10) |
C3—N2—H2 | 107.8 | N7—Na1—Cl1 | 72.91 (9) |
Co1—N2—H2 | 107.8 | O1B—Na1—Cl1 | 25.36 (7) |
C6—N3—C5 | 115.6 (3) | O1C—Na1—Cl1 | 25.61 (7) |
C6—N3—Co1 | 107.7 (2) | N6—Na1—Cl1 | 90.96 (9) |
C5—N3—Co1 | 108.7 (2) | O2F—Na1—Cl1 | 124.0 (3) |
C6—N3—H3 | 108.2 | O2G—Na1—Cl1 | 84.8 (4) |
C5—N3—H3 | 108.2 | O2B—Na1—Cl1i | 95.80 (13) |
Co1—N3—H3 | 108.2 | O1Di—Na1—Cl1i | 22.11 (7) |
C8—N4—C7 | 112.8 (3) | O2Aii—Na1—Cl1i | 113.51 (10) |
C8—N4—Co1 | 118.5 (2) | N7—Na1—Cl1i | 153.67 (10) |
C7—N4—Co1 | 106.5 (2) | O1B—Na1—Cl1i | 86.72 (9) |
C8—N4—H4 | 106.1 | O1C—Na1—Cl1i | 77.41 (8) |
C7—N4—H4 | 106.1 | N6—Na1—Cl1i | 73.19 (8) |
Co1—N4—H4 | 106.1 | O2F—Na1—Cl1i | 77.7 (5) |
C4—N5—Co1 | 100.0 (2) | O2G—Na1—Cl1i | 92.3 (4) |
C4—N5—H5C | 111.8 | Cl1—Na1—Cl1i | 84.24 (5) |
Co1—N5—H5C | 111.8 | | |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1C | 0.91 | 2.10 | 2.985 (4) | 163 |
N2—H2···N7iii | 0.91 | 2.08 | 2.983 (4) | 172 |
N3—H3···O1Aiii | 0.91 | 2.53 | 3.149 (5) | 126 |
N3—H3···N7iii | 0.91 | 2.56 | 3.384 (4) | 151 |
N4—H4···O2Aii | 0.91 | 2.25 | 3.137 (4) | 163 |
N5—H5C···O3D | 0.90 | 2.34 | 3.193 (5) | 159 |
N5—H5C···O3A | 0.90 | 2.66 | 3.246 (6) | 124 |
N5—H5D···O3Civ | 0.90 | 2.26 | 3.144 (5) | 167 |
N6—H6D···O1Bi | 0.90 | 2.60 | 3.281 (5) | 133 |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x, −y+1, −z+1. |
(II)
trans-Dicyano(
trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane- 6,13-diamine)cobalt(III)
trans-dicyano(
trans-6,13-dimethyl- 1,4,8,11-tetraazacyclotetradecane-6,13-diaminium)cobalt(III) tetraperchlorate tetrahydrate
top
Crystal data top
[Co(C14H32N8)][Co(C14H30N8)](ClO4)3·4H2O | Z = 1 |
Mr = 1210.66 | F(000) = 632 |
Triclinic, P1 | Dx = 1.603 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0697 (3) Å | Cell parameters from 25 reflections |
b = 10.5362 (5) Å | θ = 11.2–13.8° |
c = 13.3674 (9) Å | µ = 0.96 mm−1 |
α = 87.805 (6)° | T = 294 K |
β = 82.909 (7)° | Prism, yellow |
γ = 81.743 (5)° | 0.5 × 0.2 × 0.2 mm |
V = 1254.21 (11) Å3 | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 3690 reflections with I > 2σ(I) |
Radiation source: Enraf-Nonius FR590 | Rint = 0.029 |
Graphite monochromator | θmax = 25.0°, θmin = 1.5° |
non–profiled ω/2θ scans | h = 0→10 |
Absorption correction: ψ scan (North et al., 1968) Number of ψ scan sets used was 4
Theta correction was applied. Averaged transmission function
was used. No Fourier smoothing was applied. | k = −12→12 |
Tmin = 0.791, Tmax = 0.806 | l = −15→15 |
4719 measured reflections | 3 standard reflections every 120 min |
4412 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.166 | w = 1/[σ2(Fo2) + (0.09P)2 + 2.931P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
4412 reflections | Δρmax = 1.20 e Å−3 |
327 parameters | Δρmin = −0.96 e Å−3 |
37 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.044 (4) |
Crystal data top
[Co(C14H32N8)][Co(C14H30N8)](ClO4)3·4H2O | γ = 81.743 (5)° |
Mr = 1210.66 | V = 1254.21 (11) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.0697 (3) Å | Mo Kα radiation |
b = 10.5362 (5) Å | µ = 0.96 mm−1 |
c = 13.3674 (9) Å | T = 294 K |
α = 87.805 (6)° | 0.5 × 0.2 × 0.2 mm |
β = 82.909 (7)° | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 3690 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) Number of ψ scan sets used was 4
Theta correction was applied. Averaged transmission function
was used. No Fourier smoothing was applied. | Rint = 0.029 |
Tmin = 0.791, Tmax = 0.806 | 3 standard reflections every 120 min |
4719 measured reflections | intensity decay: none |
4412 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | 37 restraints |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.06 | Δρmax = 1.20 e Å−3 |
4412 reflections | Δρmin = −0.96 e Å−3 |
327 parameters | |
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 | Occ. (<1) |
Cl1 | 0.1591 (2) | 0.16830 (18) | 0.73017 (12) | 0.0775 (6) | |
O1A | 0.0080 (9) | 0.2296 (13) | 0.7623 (11) | 0.134 (6)* | 0.525 (16) |
O1B | 0.146 (2) | 0.1119 (14) | 0.6378 (7) | 0.150 (7)* | 0.525 (16) |
O1C | 0.2554 (12) | 0.2648 (9) | 0.7143 (8) | 0.075 (3)* | 0.525 (16) |
O1D | 0.2073 (14) | 0.0848 (12) | 0.8094 (8) | 0.093 (4)* | 0.525 (16) |
O1E | 0.0237 (15) | 0.1459 (19) | 0.6961 (15) | 0.178 (9)* | 0.475 (16) |
O1F | 0.1793 (17) | 0.1188 (14) | 0.8290 (7) | 0.094 (5)* | 0.475 (16) |
O1G | 0.2000 (16) | 0.2942 (8) | 0.7134 (9) | 0.080 (4)* | 0.475 (16) |
O1H | 0.2711 (18) | 0.0868 (15) | 0.6658 (12) | 0.172 (9)* | 0.475 (16) |
Cl2A | 0.6788 (3) | 0.89822 (16) | 0.8163 (3) | 0.0484 (7) | 0.734 (10) |
O2D | 0.7408 (13) | 0.8755 (12) | 0.9044 (7) | 0.172 (5)* | 0.734 (10) |
Cl2B | 0.6523 (7) | 0.9044 (5) | 0.7880 (7) | 0.065 (3)* | 0.266 (10) |
O2E | 0.5776 (19) | 0.9256 (17) | 0.7058 (11) | 0.097 (7)* | 0.266 (10) |
O2A | 0.5517 (7) | 0.9757 (6) | 0.8529 (8) | 0.193 (5) | |
O2B | 0.7842 (6) | 0.9503 (8) | 0.7585 (7) | 0.193 (5) | |
O2C | 0.6495 (10) | 0.7773 (5) | 0.8001 (5) | 0.154 (4) | |
O1 | −0.0032 (5) | 0.4632 (6) | 1.2555 (5) | 0.107 (2) | |
H1A | 0.0942 | 0.4664 | 1.2389 | 0.128* | |
H1B | −0.056 | 0.5404 | 1.2612 | 0.128* | |
O2 | 0.0784 (5) | 0.7836 (5) | 0.7297 (4) | 0.0814 (14) | |
H2A | 0.0251 | 0.8505 | 0.7032 | 0.098* | |
H2B | 0.0203 | 0.7268 | 0.7573 | 0.098* | |
C11 | 0.3880 (5) | 0.2952 (4) | 0.9228 (4) | 0.0389 (10) | |
H11A | 0.3554 | 0.2114 | 0.9324 | 0.047* | |
H11B | 0.4378 | 0.302 | 0.8547 | 0.047* | |
C21 | 0.2561 (5) | 0.3995 (4) | 0.9408 (4) | 0.0387 (10) | |
H21A | 0.1864 | 0.3954 | 0.8919 | 0.046* | |
H21B | 0.2037 | 0.3903 | 1.0079 | 0.046* | |
C31 | 0.1977 (5) | 0.6318 (4) | 0.9574 (3) | 0.0333 (9) | |
H31A | 0.1516 | 0.6162 | 1.0253 | 0.04* | |
H31B | 0.1212 | 0.6326 | 0.9126 | 0.04* | |
C41 | 0.2475 (5) | 0.7636 (4) | 0.9529 (3) | 0.0348 (10) | |
C51 | 0.6335 (5) | 0.2243 (4) | 0.9789 (3) | 0.0351 (9) | |
H51A | 0.6761 | 0.2371 | 0.9096 | 0.042* | |
H51B | 0.6095 | 0.1373 | 0.9854 | 0.042* | |
C61 | 0.1108 (6) | 0.8625 (5) | 0.9857 (4) | 0.0530 (13) | |
H61A | 0.0337 | 0.8569 | 0.9436 | 0.08* | |
H61B | 0.1393 | 0.947 | 0.9795 | 0.08* | |
H61C | 0.0738 | 0.8455 | 1.0546 | 0.08* | |
C71 | 0.3761 (4) | 0.5109 (4) | 1.1281 (3) | 0.0277 (8) | |
N11 | 0.4915 (4) | 0.3141 (3) | 0.9980 (3) | 0.0294 (7) | |
H11 | 0.4462 | 0.292 | 1.0595 | 0.035* | |
N21 | 0.3175 (4) | 0.5233 (3) | 0.9300 (2) | 0.0270 (7) | |
H21 | 0.3488 | 0.534 | 0.8633 | 0.032* | |
N31 | 0.3000 (5) | 0.7999 (4) | 0.8451 (3) | 0.0398 (9) | |
H31C | 0.2289 | 0.7922 | 0.8063 | 0.061 (18)* | |
H31D | 0.3833 | 0.748 | 0.8234 | 0.058 (17)* | |
H31E | 0.3189 | 0.8806 | 0.8422 | 0.063 (18)* | |
N41 | 0.3014 (5) | 0.5177 (4) | 1.2030 (3) | 0.0440 (9) | |
Co1 | 0.5 | 0.5 | 1 | 0.0223 (2) | |
C12 | 0.3190 (6) | 0.3180 (5) | 0.4591 (4) | 0.0480 (12) | |
H12A | 0.2654 | 0.2476 | 0.4838 | 0.058* | |
H12B | 0.3564 | 0.3042 | 0.3887 | 0.058* | |
C22 | 0.2167 (5) | 0.4428 (5) | 0.4706 (4) | 0.0471 (12) | |
H22A | 0.1389 | 0.4462 | 0.4265 | 0.057* | |
H22B | 0.1691 | 0.4511 | 0.5395 | 0.057* | |
C32 | 0.7817 (5) | 0.3262 (5) | 0.5292 (4) | 0.0463 (12) | |
H32A | 0.8715 | 0.3153 | 0.563 | 0.056* | |
H32B | 0.813 | 0.3259 | 0.4572 | 0.056* | |
C42 | 0.6966 (7) | 0.2131 (5) | 0.5574 (4) | 0.0515 (13) | |
C52 | 0.5656 (7) | 0.2143 (4) | 0.4975 (4) | 0.0482 (12) | |
H52A | 0.6023 | 0.2158 | 0.4262 | 0.058* | |
H52B | 0.5227 | 0.1355 | 0.5121 | 0.058* | |
C62 | 0.8066 (9) | 0.0899 (6) | 0.5331 (5) | 0.078 (2) | |
H62A | 0.8906 | 0.0873 | 0.5708 | 0.117* | |
H62B | 0.8414 | 0.0889 | 0.4623 | 0.117* | |
H62C | 0.7566 | 0.0165 | 0.5511 | 0.117* | |
C72 | 0.4074 (5) | 0.5413 (4) | 0.6339 (3) | 0.0299 (9) | |
N12 | 0.4457 (4) | 0.3248 (3) | 0.5187 (3) | 0.0366 (8) | |
H12 | 0.4086 | 0.3168 | 0.5848 | 0.044* | |
N22 | 0.3068 (4) | 0.5482 (4) | 0.4441 (3) | 0.0347 (8) | |
H22 | 0.3285 | 0.5489 | 0.3757 | 0.042* | |
N32 | 0.6371 (6) | 0.2241 (4) | 0.6652 (3) | 0.0585 (12) | |
H32C | 0.7129 | 0.2236 | 0.7017 | 0.088* | |
H32D | 0.5884 | 0.158 | 0.684 | 0.088* | |
N42 | 0.3591 (5) | 0.5657 (4) | 0.7144 (3) | 0.0427 (9) | |
Co2 | 0.5 | 0.5 | 0.5 | 0.0253 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.1027 (13) | 0.0910 (12) | 0.0530 (9) | −0.0546 (10) | −0.0184 (8) | 0.0010 (8) |
Cl2A | 0.0570 (12) | 0.0404 (11) | 0.0477 (13) | −0.0139 (8) | −0.0023 (11) | 0.0138 (8) |
O2A | 0.089 (5) | 0.107 (5) | 0.372 (14) | −0.018 (4) | 0.056 (6) | −0.120 (7) |
O2B | 0.064 (4) | 0.191 (8) | 0.297 (11) | −0.004 (4) | 0.019 (5) | 0.179 (8) |
O2C | 0.244 (9) | 0.066 (4) | 0.132 (5) | −0.041 (5) | 0.091 (6) | −0.027 (4) |
O1 | 0.049 (3) | 0.126 (4) | 0.148 (6) | −0.026 (3) | −0.012 (3) | 0.015 (4) |
O2 | 0.061 (3) | 0.105 (4) | 0.074 (3) | 0.012 (2) | −0.020 (2) | 0.001 (3) |
C11 | 0.046 (3) | 0.032 (2) | 0.043 (3) | −0.0110 (19) | −0.014 (2) | −0.0079 (19) |
C21 | 0.037 (2) | 0.039 (2) | 0.045 (3) | −0.0138 (19) | −0.0129 (19) | −0.001 (2) |
C31 | 0.025 (2) | 0.041 (2) | 0.032 (2) | 0.0011 (17) | −0.0010 (16) | 0.0013 (18) |
C41 | 0.036 (2) | 0.031 (2) | 0.032 (2) | 0.0089 (18) | 0.0013 (17) | −0.0024 (17) |
C51 | 0.042 (2) | 0.028 (2) | 0.033 (2) | 0.0045 (18) | −0.0033 (18) | −0.0055 (17) |
C61 | 0.050 (3) | 0.048 (3) | 0.053 (3) | 0.020 (2) | −0.001 (2) | −0.008 (2) |
C71 | 0.030 (2) | 0.028 (2) | 0.025 (2) | −0.0022 (16) | −0.0028 (16) | −0.0017 (15) |
N11 | 0.0349 (18) | 0.0247 (17) | 0.0286 (17) | −0.0037 (14) | −0.0041 (14) | −0.0013 (13) |
N21 | 0.0272 (17) | 0.0292 (17) | 0.0244 (16) | −0.0033 (13) | −0.0029 (13) | −0.0009 (13) |
N31 | 0.049 (2) | 0.035 (2) | 0.034 (2) | −0.0016 (17) | −0.0043 (17) | 0.0021 (16) |
N41 | 0.044 (2) | 0.054 (2) | 0.032 (2) | −0.0082 (19) | 0.0053 (18) | −0.0030 (17) |
Co1 | 0.0241 (4) | 0.0232 (4) | 0.0191 (4) | −0.0030 (3) | −0.0012 (3) | −0.0019 (3) |
C12 | 0.055 (3) | 0.052 (3) | 0.043 (3) | −0.025 (2) | −0.008 (2) | −0.005 (2) |
C22 | 0.037 (2) | 0.071 (3) | 0.037 (2) | −0.018 (2) | −0.007 (2) | −0.003 (2) |
C32 | 0.041 (3) | 0.057 (3) | 0.035 (2) | 0.017 (2) | −0.006 (2) | −0.004 (2) |
C42 | 0.074 (4) | 0.041 (3) | 0.032 (2) | 0.018 (2) | −0.006 (2) | 0.000 (2) |
C52 | 0.075 (4) | 0.030 (2) | 0.038 (3) | 0.001 (2) | −0.006 (2) | −0.0036 (19) |
C62 | 0.108 (5) | 0.055 (4) | 0.058 (4) | 0.039 (4) | −0.015 (4) | −0.009 (3) |
C72 | 0.031 (2) | 0.033 (2) | 0.024 (2) | 0.0003 (17) | −0.0041 (16) | −0.0007 (16) |
N12 | 0.051 (2) | 0.0337 (19) | 0.0257 (18) | −0.0105 (17) | −0.0029 (16) | −0.0007 (15) |
N22 | 0.0320 (18) | 0.046 (2) | 0.0249 (17) | 0.0012 (16) | −0.0045 (14) | −0.0027 (15) |
N32 | 0.090 (4) | 0.050 (3) | 0.031 (2) | 0.006 (2) | −0.007 (2) | 0.0035 (19) |
N42 | 0.046 (2) | 0.053 (2) | 0.026 (2) | 0.0052 (18) | −0.0024 (16) | −0.0031 (17) |
Co2 | 0.0278 (4) | 0.0290 (4) | 0.0182 (4) | −0.0019 (3) | −0.0019 (3) | −0.0018 (3) |
Geometric parameters (Å, º) top
Cl1—O1E | 1.415 (7) | N11—H11 | 0.91 |
Cl1—O1B | 1.415 (6) | N21—Co1 | 1.981 (3) |
Cl1—O1D | 1.421 (6) | C71—Co1 | 1.926 (4) |
Cl1—O1F | 1.424 (6) | N21—H21 | 0.91 |
Cl1—O1C | 1.426 (5) | N31—H31C | 0.89 |
Cl1—O1G | 1.431 (6) | N31—H31D | 0.89 |
Cl1—O1H | 1.449 (7) | N31—H31E | 0.89 |
Cl1—O1A | 1.449 (6) | Co1—C71i | 1.926 (4) |
Cl2A—O2B | 1.322 (5) | Co1—N11i | 1.972 (3) |
Cl2A—O2A | 1.362 (5) | Co1—N21i | 1.981 (3) |
Cl2A—O2D | 1.365 (6) | C12—N12 | 1.489 (6) |
Cl2A—O2C | 1.368 (5) | C12—C22 | 1.497 (8) |
Cl2B—O2A | 1.344 (6) | C12—H12A | 0.97 |
Cl2B—O2C | 1.346 (6) | C12—H12B | 0.97 |
Cl2B—O2E | 1.356 (6) | C22—N22 | 1.478 (6) |
Cl2B—O2B | 1.362 (5) | C22—H22A | 0.97 |
O1—H1A | 0.8885 | C22—H22B | 0.97 |
O1—H1B | 0.8842 | C32—N22ii | 1.478 (6) |
O2—H2A | 0.8832 | C32—C42 | 1.522 (8) |
O2—H2B | 0.8934 | C32—H32A | 0.97 |
C11—N11 | 1.495 (5) | C32—H32B | 0.97 |
C11—C21 | 1.506 (7) | C42—N32 | 1.478 (6) |
C11—H11A | 0.97 | C42—C52 | 1.510 (8) |
C11—H11B | 0.97 | C42—C62 | 1.538 (7) |
C21—N21 | 1.486 (5) | C52—N12 | 1.485 (6) |
C21—H21A | 0.97 | C52—H52A | 0.97 |
C21—H21B | 0.97 | C52—H52B | 0.97 |
C31—N21 | 1.482 (5) | C62—H62A | 0.96 |
C31—C41 | 1.518 (6) | C62—H62B | 0.96 |
C31—H31A | 0.97 | C62—H62C | 0.96 |
C31—H31B | 0.97 | C72—N42 | 1.136 (6) |
C41—N31 | 1.514 (6) | N12—Co2 | 1.977 (4) |
C41—C51i | 1.518 (6) | N12—H12 | 0.91 |
C41—C61 | 1.530 (6) | N22—C32ii | 1.478 (6) |
C51—N11 | 1.486 (5) | N22—Co2 | 1.982 (3) |
C51—C41i | 1.518 (6) | C72—Co2 | 1.918 (4) |
C51—H51A | 0.97 | N22—H22 | 0.91 |
C51—H51B | 0.97 | N32—H32C | 0.89 |
C61—H61A | 0.96 | N32—H32D | 0.89 |
C61—H61B | 0.96 | Co2—C72ii | 1.918 (4) |
C61—H61C | 0.96 | Co2—N12ii | 1.977 (4) |
C71—N41 | 1.136 (6) | Co2—N22ii | 1.982 (3) |
N11—Co1 | 1.972 (3) | | |
| | | |
O1B—Cl1—O1D | 117.4 (8) | C71—Co1—N11 | 90.15 (15) |
O1E—Cl1—O1F | 114.3 (9) | C71i—Co1—N11 | 89.85 (15) |
O1B—Cl1—O1C | 110.6 (7) | C71—Co1—N11i | 89.85 (15) |
O1D—Cl1—O1C | 108.2 (7) | C71i—Co1—N11i | 90.15 (15) |
O1E—Cl1—O1G | 117.1 (9) | N11—Co1—N11i | 180.0000 (10) |
O1F—Cl1—O1G | 112.7 (7) | C71—Co1—N21 | 89.85 (15) |
O1E—Cl1—O1H | 102.4 (9) | C71i—Co1—N21 | 90.15 (15) |
O1F—Cl1—O1H | 103.5 (9) | N11—Co1—N21 | 86.81 (14) |
O1G—Cl1—O1H | 104.7 (8) | N11i—Co1—N21 | 93.19 (14) |
O1B—Cl1—O1A | 103.6 (8) | C71—Co1—N21i | 90.15 (15) |
O1D—Cl1—O1A | 108.2 (7) | C71i—Co1—N21i | 89.85 (15) |
O1C—Cl1—O1A | 108.5 (7) | N11—Co1—N21i | 93.19 (14) |
O2B—Cl2A—O2A | 118.4 (5) | N11i—Co1—N21i | 86.81 (14) |
O2B—Cl2A—O2D | 102.0 (7) | N21—Co1—N21i | 180.0000 (10) |
O2A—Cl2A—O2D | 98.1 (7) | N12—C12—C22 | 107.5 (4) |
O2B—Cl2A—O2C | 121.6 (6) | N12—C12—H12A | 110.2 |
O2A—Cl2A—O2C | 111.3 (5) | C22—C12—H12A | 110.2 |
O2D—Cl2A—O2C | 99.3 (6) | N12—C12—H12B | 110.2 |
O2A—Cl2B—O2C | 113.8 (6) | C22—C12—H12B | 110.2 |
O2A—Cl2B—O2E | 97.7 (9) | H12A—C12—H12B | 108.5 |
O2C—Cl2B—O2E | 98.9 (9) | N22—C22—C12 | 108.4 (4) |
O2A—Cl2B—O2B | 116.9 (6) | N22—C22—H22A | 110 |
O2C—Cl2B—O2B | 120.3 (6) | C12—C22—H22A | 110 |
O2E—Cl2B—O2B | 103.4 (9) | N22—C22—H22B | 110 |
H1A—O1—H1B | 112.3 | C12—C22—H22B | 110 |
H2A—O2—H2B | 111.6 | H22A—C22—H22B | 108.4 |
N11—C11—C21 | 106.1 (3) | N22ii—C32—C42 | 113.6 (4) |
N11—C11—H11A | 110.5 | N22ii—C32—H32A | 108.8 |
C21—C11—H11A | 110.5 | C42—C32—H32A | 108.8 |
N11—C11—H11B | 110.5 | N22ii—C32—H32B | 108.8 |
C21—C11—H11B | 110.5 | C42—C32—H32B | 108.8 |
H11A—C11—H11B | 108.7 | H32A—C32—H32B | 107.7 |
N21—C21—C11 | 106.6 (3) | N32—C42—C52 | 108.1 (5) |
N21—C21—H21A | 110.4 | N32—C42—C32 | 107.4 (4) |
C11—C21—H21A | 110.4 | C52—C42—C32 | 112.0 (4) |
N21—C21—H21B | 110.4 | N32—C42—C62 | 113.7 (4) |
C11—C21—H21B | 110.4 | C52—C42—C62 | 108.3 (5) |
H21A—C21—H21B | 108.6 | C32—C42—C62 | 107.4 (5) |
N21—C31—C41 | 115.8 (3) | N12—C52—C42 | 113.9 (4) |
N21—C31—H31A | 108.3 | N12—C52—H52A | 108.8 |
C41—C31—H31A | 108.3 | C42—C52—H52A | 108.8 |
N21—C31—H31B | 108.3 | N12—C52—H52B | 108.8 |
C41—C31—H31B | 108.3 | C42—C52—H52B | 108.8 |
H31A—C31—H31B | 107.4 | H52A—C52—H52B | 107.7 |
N31—C41—C51i | 110.8 (4) | C42—C62—H62A | 109.5 |
N31—C41—C31 | 110.1 (3) | C42—C62—H62B | 109.5 |
C51i—C41—C31 | 113.7 (3) | H62A—C62—H62B | 109.5 |
N31—C41—C61 | 105.7 (4) | C42—C62—H62C | 109.5 |
C51i—C41—C61 | 107.8 (4) | H62A—C62—H62C | 109.5 |
C31—C41—C61 | 108.5 (4) | H62B—C62—H62C | 109.5 |
N11—C51—C41i | 116.0 (3) | N42—C72—Co2 | 176.8 (4) |
N11—C51—H51A | 108.3 | C52—N12—C12 | 110.9 (4) |
C41i—C51—H51A | 108.3 | C52—N12—Co2 | 118.4 (3) |
N11—C51—H51B | 108.3 | C12—N12—Co2 | 107.3 (3) |
C41i—C51—H51B | 108.3 | C52—N12—H12 | 106.5 |
H51A—C51—H51B | 107.4 | C12—N12—H12 | 106.5 |
C41—C61—H61A | 109.5 | Co2—N12—H12 | 106.5 |
C41—C61—H61B | 109.5 | C22—N22—C32ii | 111.0 (4) |
H61A—C61—H61B | 109.5 | C22—N22—Co2 | 107.1 (3) |
C41—C61—H61C | 109.5 | C32ii—N22—Co2 | 118.3 (3) |
H61A—C61—H61C | 109.5 | C22—N22—H22 | 106.6 |
H61B—C61—H61C | 109.5 | C32ii—N22—H22 | 106.6 |
N41—C71—Co1 | 179.1 (4) | Co2—N22—H22 | 106.6 |
C51—N11—C11 | 110.1 (3) | C42—N32—H32C | 109.3 |
C51—N11—Co1 | 119.2 (3) | C42—N32—H32D | 109.2 |
C11—N11—Co1 | 106.6 (2) | H32C—N32—H32D | 109.5 |
C51—N11—H11 | 106.8 | C72—Co2—C72ii | 180.0000 (10) |
C11—N11—H11 | 106.8 | C72—Co2—N12 | 90.09 (16) |
Co1—N11—H11 | 106.8 | C72ii—Co2—N12 | 89.91 (16) |
C31—N21—C21 | 110.7 (3) | C72—Co2—N12ii | 89.91 (16) |
C31—N21—Co1 | 119.4 (3) | C72ii—Co2—N12ii | 90.09 (16) |
C21—N21—Co1 | 106.6 (2) | N12—Co2—N12ii | 180.0 (2) |
C31—N21—H21 | 106.5 | C72—Co2—N22ii | 88.44 (16) |
C21—N21—H21 | 106.5 | C72ii—Co2—N22ii | 91.56 (16) |
Co1—N21—H21 | 106.5 | N12—Co2—N22ii | 93.14 (16) |
C41—N31—H31C | 109.5 | N12ii—Co2—N22ii | 86.86 (16) |
C41—N31—H31D | 109.5 | C72—Co2—N22 | 91.56 (16) |
H31C—N31—H31D | 109.5 | C72ii—Co2—N22 | 88.44 (16) |
C41—N31—H31E | 109.5 | N12—Co2—N22 | 86.86 (16) |
H31C—N31—H31E | 109.5 | N12ii—Co2—N22 | 93.14 (16) |
H31D—N31—H31E | 109.5 | N22ii—Co2—N22 | 180 |
C71—Co1—C71i | 180.0000 (10) | | |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N41 | 0.89 | 2.03 | 2.898 (6) | 167 |
O1—H1B···O1Giii | 0.88 | 2.03 | 2.912 (14) | 172 |
O2—H2B···O1iii | 0.89 | 2.05 | 2.776 (9) | 138 |
N11—H11···O2Ci | 0.91 | 2.12 | 3.024 (7) | 175 |
N21—H21···N42 | 0.91 | 2.00 | 2.885 (5) | 165 |
N31—H31C···O2 | 0.89 | 1.82 | 2.708 (6) | 177 |
N31—H31E···O2A | 0.89 | 2.49 | 3.153 (8) | 132 |
N31—H31E···O1Div | 0.89 | 2.29 | 3.035 (12) | 141 |
N31—H31E···O1Fiv | 0.89 | 2.65 | 3.388 (15) | 141 |
N12—H12···O1C | 0.91 | 2.19 | 3.048 (10) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (iii) −x, −y+1, −z+2; (iv) x, y+1, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | Na[Co(C13H30N7)](ClO4)3 | [Co(C14H32N8)][Co(C14H30N8)](ClO4)3·4H2O |
Mr | 664.71 | 1210.66 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 294 | 294 |
a, b, c (Å) | 9.405 (2), 10.683 (2), 14.211 (2) | 9.0697 (3), 10.5362 (5), 13.3674 (9) |
α, β, γ (°) | 94.02 (1), 100.62 (2), 111.21 (1) | 87.805 (6), 82.909 (7), 81.743 (5) |
V (Å3) | 1293.7 (4) | 1254.21 (11) |
Z | 2 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.06 | 0.96 |
Crystal size (mm) | 0.27 × 0.27 × 0.07 | 0.5 × 0.2 × 0.2 |
|
Data collection |
Diffractometer | Enraf-Nonius TurboCAD4 diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) Number of ψ scan sets used was 4
Theta correction was applied. Averaged transmission function
was used. No Fourier smoothing was applied. | ψ scan (North et al., 1968) Number of ψ scan sets used was 4
Theta correction was applied. Averaged transmission function
was used. No Fourier smoothing was applied. |
Tmin, Tmax | 0.799, 0.928 | 0.791, 0.806 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4846, 4546, 3275 | 4719, 4412, 3690 |
Rint | 0.018 | 0.029 |
(sin θ/λ)max (Å−1) | 0.594 | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.110, 1.02 | 0.059, 0.166, 1.06 |
No. of reflections | 4546 | 4412 |
No. of parameters | 348 | 327 |
No. of restraints | 9 | 37 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.43 | 1.20, −0.96 |
Selected bond lengths (Å) for (I) topCo1—N1 | 1.949 (3) | O1B—Na1 | 2.663 (4) |
Co1—N2 | 1.944 (3) | O1C—Na1 | 2.746 (4) |
Co1—N3 | 1.953 (3) | O1D—Na1i | 2.383 (3) |
Co1—N4 | 1.969 (3) | O2A—Na1ii | 2.480 (4) |
Co1—N5 | 1.986 (3) | O2B—Na1 | 2.331 (5) |
C13—Co1 | 1.899 (3) | O2F—Na1 | 2.99 (3) |
N6—Na1 | 2.920 (4) | O2G—Na1 | 3.01 (3) |
N7—Na1 | 2.574 (3) | | |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y, −z+2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1C | 0.91 | 2.10 | 2.985 (4) | 163 |
N2—H2···N7iii | 0.91 | 2.08 | 2.983 (4) | 172 |
N3—H3···O1Aiii | 0.91 | 2.53 | 3.149 (5) | 126 |
N3—H3···N7iii | 0.91 | 2.56 | 3.384 (4) | 151 |
N4—H4···O2Aii | 0.91 | 2.25 | 3.137 (4) | 163 |
N5—H5C···O3D | 0.90 | 2.34 | 3.193 (5) | 159 |
N5—H5C···O3A | 0.90 | 2.66 | 3.246 (6) | 124 |
N5—H5D···O3Civ | 0.90 | 2.26 | 3.144 (5) | 167 |
N6—H6D···O1Bi | 0.90 | 2.60 | 3.281 (5) | 133 |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x, −y+1, −z+1. |
Selected bond lengths (Å) for (II) topN11—Co1 | 1.972 (3) | N12—Co2 | 1.977 (4) |
N21—Co1 | 1.981 (3) | N22—Co2 | 1.982 (3) |
C71—Co1 | 1.926 (4) | C72—Co2 | 1.918 (4) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N41 | 0.89 | 2.03 | 2.898 (6) | 167 |
O1—H1B···O1Gi | 0.88 | 2.03 | 2.912 (14) | 172 |
O2—H2B···O1i | 0.89 | 2.05 | 2.776 (9) | 138 |
N11—H11···O2Cii | 0.91 | 2.12 | 3.024 (7) | 175 |
N21—H21···N42 | 0.91 | 2.00 | 2.885 (5) | 165 |
N31—H31C···O2 | 0.89 | 1.82 | 2.708 (6) | 177 |
N31—H31E···O2A | 0.89 | 2.49 | 3.153 (8) | 132 |
N31—H31E···O1Diii | 0.89 | 2.29 | 3.035 (12) | 141 |
N31—H31E···O1Fiii | 0.89 | 2.65 | 3.388 (15) | 141 |
N12—H12···O1C | 0.91 | 2.19 | 3.048 (10) | 158 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+2; (iii) x, y+1, z. |
The attachment of potentially coordinating functional groups, such as primary amines, to the periphery of macrocyclic ligands, so-called pendent-arm macrocycles, brings an added dimension to the coordination chemistry of the macrocycle. For example, the well studied macrocyclic tetraamine 1,4,8,11-tetraazacycloctetradecane (cyclam) may at best occupy four coordination sites on a given metal. However, the introduction of two exocyclic primary amines to give the analogue trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L) can be achieved easily using a metal-templated synthesis (Comba et al., 1986; Bernhardt et al., 1989) The cis isomer of L is also known (Bernhardt et al., 1992, 1993). The ligand L is quite versatile and has been shown to bind in a hexadentate (Bernhardt et al., 1989, 1991, 1997; Bernhardt, Comba et al., 1990), pentadentate (Bernhardt, Lawrance, Comba et al., 1990; Curtis et al., 1992; Curtis et al., 1993) or tetradentate (Comba et al., 1986; Bernhardt, Lawrance, Patalinghug et al. 1990; Bernhardt et al., 1997) mode, depending on whether both, one or no primary amines are coordinated, respectively. The mode of coordination is governed by the metal ion preferences, the synthetic procedures (heat, solvent) and the presence of competing ligands. Here, we report the structures of two cobalt(III) complexes, one bearing the ligand bound in a pentadentate mode, (I), and the other bound in a tetradentate mode, (II). Cyano ligands complete the pseudo-octahedral coordination geometries. These structures are compared with related cyano complexes of CoIII, and also with the hexadentate-coordinated analogue [CoL]3+.
The structure of Na{trans-[CoL(CN)](ClO4)3, (I), finds all molecules on general sites. The geometry of the Co complex is shown in Fig. 1. Pentadentate coordination of the macrocycle is apparent and a C-bound cyano ligand occupies the coordination site trans to the single coordinated primary amine (N5). The configuration of the four macrocyclic amines is RSRS, which is commonly referred to as trans-I. Interestingly, it is this N-based configurational isomer that has been observed in nearly all structurally characterized complexes of pentadentate-coordinated L. The macrocyclic Co—N bond lengths (Table 1) are all similar but significantly shorter than the coordinate bond to the pendent amine N5. This is a consequence of a trans influence of the cyano ligand, which has been shown to elongate the trans-disposed Co—N bond lengths in similar compounds (Bernhardt & Hayes, 2002; Bernhardt & Macpherson, 2003). Similar trans influences are well known in CoIII chemistry, and other examples include the elongation of Co—O coordinate bonds trans to cyano in mixed ligand cyano β-diketonate phosphine complexes (Kita et al., 1988; Suzuki et al., 1998).
The Na+ cation is seven-coordinate and is bound to both the complex cation and the perchlorate anions in a variety of modes (Fig. 2). The Na+ ion forms bonds to the cyano N atom (N7) and the dangling pendent amine (N6) in an unusual chelation mode. The remaining coordination sites are occupied by a pair of O atoms from a bidentate-coordinated perchlorate (O1B and O1C), and three monodentate-coordinated perchlorates (O2B, O2Aii and O1Di; see Table 1 for symmetry codes). Both perchlorates bridge adjacent Na+ cations, with the result being a linear Na+/ClO4− coordination polymer with Co complex side-chains. These side chains are cross-linked by pairs of symmetry-related perchlorate anions which form hydrogen-bonded bridges between the coordinated primary amine H atoms.
Although perchlorates 1 and 3 are well ordered, perchlorate 2 was found to be rotationally disordered about the O2A—Cl2 bond. Significantly, an N4—H4···O2A hydrogen bond and an Na1—O2A coordinate bond anchor this pivotal O atom, whilst the other three O atoms were refined in two different positions, with the aid of tetrahedral restraints for the minor component. The two contributors to this disorder each form bridging coordinate bonds between adjacent Na atoms (Na1—O2B 88%/Na1—O2F 12%) although the Na—O2F distance in the minor component is much longer. The other O atoms, O2C/O2G and O2D/O2E, do not form any significant hydrogen bonds or coordinate bonds, which allows the anion to adopt two alterative orientations within the structure.
Given that many of the perchlorate O atoms are coordinated to the Na+ ion, there are relatively few strong hydrogen-bonding interactions (Table 2). One notable interaction is a pair of symmetry-related N2—H2···N7iii interactions which link the Co complexes into hydrogen-bonded dimers. The non-coordinated perchlorate O atoms participate exclusively in hydrogen bonds with the coordinated primary amine (N5), which link the above-mentioned hydrogen-bonded dimers.
The structure of the tetradentate-coordinated macrocyclic complex trans-[CoL(CN)2]trans-[Co(H2L)(CN)2](ClO4)4·4H2O, (II), comprises two independent complex cations each on a centre of symmetry, in addition to perchlorate anions and water molecules on general sites. Both unique perchlorate anions were found to be disordered. Both complex cations exhibit a tetragonally compressed octahedral coordination geometry.
Analysis of difference maps during refinement revealed that atom N31 bears three H atoms, i.e. the complex containing Co1 (cation 1) is in its diprotonated form, trans-[Co(H2L)(CN)2]3+ (Fig. 3), while atom N32 of cation 2 possesses only two H atoms, corresponding with a formula trans-[CoL(CN)2]+ (Fig 4). This is consistent with two whole perchlorate anions in the asymmetric unit. In both complex cations, the macrocycle is coordinated in the so-called trans-III configuration of N-donors, and the pendent amines are cis to the adjacent secondary amine H atoms.
The coordinate bond lengths and angles of trans-[Co(H2L)(CN)2]3+ and trans-[CoL(CN)2]+ are very similar (Table 3). The Co—N bond lengths are significantly longer than those found in pentadentate-coordinated (I) and also in the hexadentate-coordinated analogue [CoL]3+, which span the range 1.937 (2)–1.955 (3) Å (Bernhardt et al., 1989; Bernhardt & Jones, 1998). This reflects a greater flexibility in the tetradentate-coordinated ligands in (II), as opposed to the rigidity imposed by coordination of the pendent amines in one or two axial sites. Indeed, it has been shown that hexadentate-coordinated complexes of L invariably exhibit abnormally short M—N bond lengths (Bernhardt et al., 1989, 1991; Bernhardt, Comba et al., 1990), and this has been reproduced by molecular mechanics calculations (Bernhardt & Comba, 1991).
The Co—CN coordinate bond lengths in (II) [1.918 (4) and 1.926 (4) Å] are lengthened significantly in comparison with that found in (I) [1.899 (3) Å]. As mentioned above, the cyano ligand exhibits a strong trans influence and in this case leads to a mutual weakening of the trans axially coordinated cyano ligands.
Although the coordination environments of the two independent cations of (II) are very similar, there are some notable disparities in the two sets of macrocyclic bond angles, particularly in the vicinity of the pendent amine/ammonio group. This is most readily seen in the angles subtended at the tertiary C atoms C41 (cation 1) and C42 (cation 2) by the methyl and ammonio/amine substituents. The N31—C41—C61 angle in the diprotonated cation trans-[Co(H2L)(CN)2]3+ [105.7 (4)°] is contracted considerably from its ideal tetrahedral value. In contrast, the corresponding N32—C42—C62 angle in the unprotonated cation trans-[CoL(CN)2]+ [113.7 (4)°] is more obtuse than its ideal value. A comparison of Figs. 3 and 4 enables the effect of these distortions to be seen clearly. Although both atoms N31 and N32 are axially disposed, the ammonio group in cation 1 (Fig. 3) is evidently distorted from an ideal axial orientation. It appears that repulsions between the secondary amine H atoms and the adjacent ammonio H atom in trans-[Co(H2L)(CN)2]3+ force the pendent ammonio group away from the cyano ligand and consequently towards the geminal methyl group. In the absence of this H atom {in trans-[CoL(CN)2]+}, no repulsive force is present and a weak attractive hydrogen bond between the pendent amine and the two adjacent secondary amine H atoms appears to draw the pendent amine closer to the axially coordinated ligand, thus opening up the N32—C42—C62 angle.
Intermolecular hydrogen bonds abound in (II), involving both complex cations, water molecules and perchlorate anions. Of note are the hydrogen bonds linking the two complex cations (Fig. 5). As seen in the structure of trans-[CoL(CN)]2+, the terminal N atoms of the cyano ligands accept hydrogen bonds from the macrocyclic secondary amine of the adjacent complex cation. These are augmented by weaker (acute) hydrogen bonds from the ammonium group (N31) on cation 1.
In conclusion, a pair of cobalt(III) complexes each bearing the hexaamine macrocycle L in a penta- or tetradentate coordinated form have been structurally characterized. The cyano ligands coordinate in the coordination sites left vacant by the pendent amines. The restraints imposed by coordination of the pendent amine in (I) lead to shorter Co—N bond lengths, and a trans influence of the cyano ligand is seen in both (I) and (II), which results in an elongation of the Co—N or Co—CN coordinate bond relative to bond lengths where an amine is coordinated in the trans position.