Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104033943/hj1035sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104033943/hj1035Isup2.hkl |
CCDC reference: 268078
All chemicals were of reagent grade, commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification. The ligand L (5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetracyclotetradiene) was synthesized according to the method of Li (1987). To a mixed solution of cyclohexane (150 ml) and ether (300 ml) containing benzoyl acetone (32.4 g, 0.2 mol) and ethylenediamine (12 g, 0.2 mol) was added anhydrous K2CO3 (41.4 g, 0.3 mol). The solution was stirred and refluxed for 5 h, and then filtered. The filtrate was evaporated, and the remains obtained were diffused with ether and refrigerated over night. The resulting light-yellow solid was filtered and washed with ether. Recrystallization of the solid from petroleum ether yielded white flaky crystals (yield 55%). L (1.9 g, 5 mmol) and Cu(ClO4)2·6H2O (1.9 g, 5 mmol) were dissolved in methanol (75 ml), and the solution was stirred and refluxed for 2 h. The red solid that precipitated was filtered and recrystallized from methanol. Red crystals of CuL(ClO4)2 were obtained. To a solution of CuL(ClO4)2 (0.6 mmol) in DMF/water (30 ml) was added K3[Co(CN)6] (0.4 mmol) in DMF/water (10 ml). Purple microcrystals precipitated from the resulting purple solution after 10 min, and these were collected by suction filtration, thoroughly washed with water and dried in air. Well shaped purple–brown crystals suitable for X-ray structure analysis were grown at room temperture by the slow diffusion of solutions of CuL(ClO4)2 and K3[Co(CN)6] in DMF/water in an H-tube. Analysis calculated for C87H109Co2Cu3N25O4: C 54.42, H 6.05, N 18.34%; found (%): C 54.58, H 6.34, N 18.43%.
H atoms attached to C atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms [Csp3—H = 0.96 Å, with Uiso(H) = 1.5Ueq(C); for H atoms in phenyl, methene (–CH2–) and methine groups C—H = 0.93, 0.97 or 0.98 Å, with Uiso(H) = 1.2Ueq(C); N—H = 0.91 Å, with Uiso(H) = 1.2Ueq(N). H atoms attached to water O atoms were located in difference Fourier maps and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(O). The O—H distances are in the range 0.7704–0.9705 Å. The DMF molecule was included with an occupancy of 0.5.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
[Cu3Co2(CN)6(C26H32N6)3]·C3H7NO·3H2O | Z = 1 |
Mr = 1877.47 | F(000) = 979 |
Triclinic, P1 | Dx = 1.299 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2510 (3) Å | Cell parameters from 5807 reflections |
b = 16.4054 (5) Å | θ = 2.3–25.1° |
c = 17.8005 (5) Å | µ = 1.05 mm−1 |
α = 113.016 (1)° | T = 293 K |
β = 93.684 (1)° | Block, purple |
γ = 101.966 (1)° | 0.56 × 0.42 × 0.26 mm |
V = 2400.55 (13) Å3 |
Siemens SMART CCD diffractometer | 8189 independent reflections |
Radiation source: fine-focus sealed tube | 6842 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | h = −11→10 |
Tmin = 0.590, Tmax = 0.772 | k = −19→17 |
12146 measured reflections | l = −21→21 |
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)] = 0.076 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.200 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0864P)2 + 7.5968P] where P = (Fo2 + 2Fc2)/3 |
8189 reflections | (Δ/σ)max < 0.001 |
557 parameters | Δρmax = 1.10 e Å−3 |
2 restraints | Δρmin = −0.76 e Å−3 |
[Cu3Co2(CN)6(C26H32N6)3]·C3H7NO·3H2O | γ = 101.966 (1)° |
Mr = 1877.47 | V = 2400.55 (13) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.2510 (3) Å | Mo Kα radiation |
b = 16.4054 (5) Å | µ = 1.05 mm−1 |
c = 17.8005 (5) Å | T = 293 K |
α = 113.016 (1)° | 0.56 × 0.42 × 0.26 mm |
β = 93.684 (1)° |
Siemens SMART CCD diffractometer | 8189 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | 6842 reflections with I > 2σ(I) |
Tmin = 0.590, Tmax = 0.772 | Rint = 0.030 |
12146 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 2 restraints |
wR(F2) = 0.200 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.10 e Å−3 |
8189 reflections | Δρmin = −0.76 e Å−3 |
557 parameters |
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) | |
Co | 0.55270 (8) | 0.17831 (5) | 0.31724 (4) | 0.0357 (2) | |
Cu1 | 0.5000 | 0.0000 | 0.5000 | 0.0449 (3) | |
Cu2 | 0.5000 | 0.0000 | 0.0000 | 0.0447 (3) | |
Cu3 | 0.5000 | 0.5000 | 0.5000 | 0.0409 (3) | |
N1 | 0.3508 (5) | 0.0635 (3) | 0.5583 (3) | 0.0433 (10) | |
N2 | 0.6667 (5) | 0.1146 (3) | 0.5373 (3) | 0.0435 (10) | |
H2C | 0.6614 | 0.1378 | 0.4987 | 0.052* | |
N3 | 0.3584 (5) | 0.0793 (3) | 0.0303 (3) | 0.0420 (10) | |
N4 | 0.6787 (5) | 0.1021 (3) | 0.0155 (3) | 0.0458 (11) | |
H4D | 0.7233 | 0.1244 | 0.0691 | 0.055* | |
N5 | 0.2875 (5) | 0.4346 (3) | 0.4527 (3) | 0.0426 (10) | |
N6 | 0.5587 (5) | 0.4978 (3) | 0.3910 (3) | 0.0447 (10) | |
H6B | 0.5883 | 0.4454 | 0.3657 | 0.054* | |
N41 | 0.4186 (7) | 0.0344 (4) | 0.3781 (4) | 0.0631 (14) | |
N42 | 0.5705 (7) | 0.0346 (4) | 0.1499 (3) | 0.0620 (14) | |
N43 | 0.5426 (7) | 0.3435 (4) | 0.4715 (3) | 0.0674 (16) | |
N44 | 0.8571 (6) | 0.1742 (4) | 0.3889 (4) | 0.0624 (14) | |
N45 | 0.7111 (7) | 0.3306 (5) | 0.2726 (4) | 0.0719 (17) | |
N46 | 0.2397 (7) | 0.1708 (5) | 0.2461 (4) | 0.0705 (16) | |
C1 | 0.1936 (6) | −0.0843 (4) | 0.4645 (4) | 0.0526 (14) | |
H1A | 0.1097 | −0.1333 | 0.4601 | 0.063* | |
H1B | 0.1761 | −0.0686 | 0.4181 | 0.063* | |
C2 | 0.2070 (7) | −0.0024 (4) | 0.5440 (4) | 0.0560 (15) | |
H2A | 0.1256 | 0.0258 | 0.5412 | 0.067* | |
H2B | 0.2009 | −0.0210 | 0.5894 | 0.067* | |
C3 | 0.3665 (6) | 0.1481 (4) | 0.5995 (3) | 0.0462 (13) | |
C4 | 0.2457 (8) | 0.1917 (5) | 0.6368 (5) | 0.0693 (19) | |
H4A | 0.1672 | 0.1464 | 0.6417 | 0.104* | |
H4B | 0.2058 | 0.2167 | 0.6019 | 0.104* | |
H4C | 0.2868 | 0.2398 | 0.6906 | 0.104* | |
C5 | 0.5127 (7) | 0.2159 (4) | 0.6132 (5) | 0.0593 (16) | |
H5A | 0.5187 | 0.2685 | 0.6646 | 0.071* | |
H5B | 0.5102 | 0.2366 | 0.5692 | 0.071* | |
C6 | 0.6565 (6) | 0.1855 (4) | 0.6172 (4) | 0.0507 (14) | |
H6A | 0.6546 | 0.1590 | 0.6579 | 0.061* | |
C7 | 0.7881 (7) | 0.2700 (4) | 0.6487 (4) | 0.0520 (14) | |
C8 | 0.8736 (8) | 0.2989 (5) | 0.7255 (4) | 0.0664 (18) | |
H8A | 0.8566 | 0.2640 | 0.7560 | 0.080* | |
C9 | 0.9853 (9) | 0.3808 (6) | 0.7568 (5) | 0.077 (2) | |
H9A | 1.0448 | 0.3991 | 0.8076 | 0.092* | |
C10 | 1.0084 (8) | 0.4338 (5) | 0.7146 (5) | 0.071 (2) | |
H10A | 1.0807 | 0.4893 | 0.7373 | 0.085* | |
C11 | 0.9260 (8) | 0.4060 (5) | 0.6387 (5) | 0.0645 (18) | |
H11A | 0.9425 | 0.4426 | 0.6097 | 0.077* | |
C12 | 0.8177 (7) | 0.3235 (4) | 0.6044 (4) | 0.0553 (15) | |
H12A | 0.7647 | 0.3039 | 0.5516 | 0.066* | |
C13 | 0.2161 (7) | −0.0584 (4) | 0.0355 (5) | 0.0587 (16) | |
H13A | 0.2498 | −0.0433 | 0.0932 | 0.070* | |
H13B | 0.1176 | −0.1006 | 0.0190 | 0.070* | |
C14 | 0.2079 (7) | 0.0257 (4) | 0.0252 (5) | 0.0600 (17) | |
H14A | 0.1492 | 0.0095 | −0.0281 | 0.072* | |
H14B | 0.1589 | 0.0618 | 0.0680 | 0.072* | |
C15 | 0.3835 (7) | 0.1657 (4) | 0.0511 (3) | 0.0453 (13) | |
C16 | 0.2664 (9) | 0.2187 (5) | 0.0728 (5) | 0.0686 (19) | |
H16A | 0.2265 | 0.2128 | 0.1194 | 0.103* | |
H16B | 0.1872 | 0.1950 | 0.0264 | 0.103* | |
H16C | 0.3106 | 0.2821 | 0.0864 | 0.103* | |
C17 | 0.5368 (7) | 0.2210 (4) | 0.0568 (4) | 0.0565 (15) | |
H17A | 0.5850 | 0.2451 | 0.1139 | 0.068* | |
H17B | 0.5250 | 0.2732 | 0.0462 | 0.068* | |
C18 | 0.6456 (7) | 0.1797 (4) | 0.0032 (4) | 0.0540 (14) | |
H18A | 0.5959 | 0.1555 | −0.0542 | 0.065* | |
C19 | 0.7822 (7) | 0.2551 (4) | 0.0132 (4) | 0.0528 (14) | |
C20 | 0.7900 (11) | 0.2912 (5) | −0.0434 (5) | 0.081 (2) | |
H20A | 0.7151 | 0.2674 | −0.0893 | 0.097* | |
C21 | 0.9080 (14) | 0.3630 (7) | −0.0335 (7) | 0.102 (3) | |
H21A | 0.9107 | 0.3884 | −0.0719 | 0.122* | |
C22 | 1.0206 (11) | 0.3972 (6) | 0.0317 (6) | 0.086 (3) | |
H22A | 1.1031 | 0.4431 | 0.0360 | 0.104* | |
C23 | 1.0125 (9) | 0.3643 (5) | 0.0903 (5) | 0.073 (2) | |
H23A | 1.0875 | 0.3893 | 0.1363 | 0.088* | |
C24 | 0.8926 (8) | 0.2934 (5) | 0.0821 (5) | 0.0693 (19) | |
H24A | 0.8862 | 0.2715 | 0.1230 | 0.083* | |
C25 | 0.3083 (7) | 0.4261 (5) | 0.5847 (4) | 0.0568 (16) | |
H25A | 0.2582 | 0.4319 | 0.6321 | 0.068* | |
H25B | 0.3377 | 0.3688 | 0.5662 | 0.068* | |
C26 | 0.2042 (7) | 0.4252 (5) | 0.5176 (4) | 0.0596 (17) | |
H26A | 0.1267 | 0.3682 | 0.4946 | 0.071* | |
H26B | 0.1567 | 0.4752 | 0.5394 | 0.071* | |
C27 | 0.2233 (6) | 0.4017 (4) | 0.3777 (3) | 0.0428 (12) | |
C28 | 0.0632 (8) | 0.3493 (5) | 0.3481 (4) | 0.0654 (18) | |
H28A | 0.0385 | 0.3085 | 0.3747 | 0.098* | |
H28B | 0.0478 | 0.3145 | 0.2893 | 0.098* | |
H28C | 0.0003 | 0.3911 | 0.3613 | 0.098* | |
C29 | 0.3072 (7) | 0.4115 (4) | 0.3108 (3) | 0.0516 (14) | |
H29A | 0.2354 | 0.4094 | 0.2675 | 0.062* | |
H29B | 0.3470 | 0.3583 | 0.2872 | 0.062* | |
C30 | 0.4348 (6) | 0.4958 (4) | 0.3337 (3) | 0.0461 (13) | |
H30A | 0.3954 | 0.5483 | 0.3644 | 0.055* | |
C31 | 0.4755 (6) | 0.5065 (4) | 0.2564 (3) | 0.0433 (12) | |
C32 | 0.4028 (8) | 0.5564 (4) | 0.2273 (4) | 0.0603 (16) | |
H32A | 0.3302 | 0.5816 | 0.2550 | 0.072* | |
C33 | 0.4359 (11) | 0.5694 (5) | 0.1576 (5) | 0.077 (2) | |
H33A | 0.3848 | 0.6020 | 0.1379 | 0.093* | |
C34 | 0.5455 (10) | 0.5335 (6) | 0.1178 (4) | 0.072 (2) | |
H34A | 0.5723 | 0.5449 | 0.0727 | 0.087* | |
C35 | 0.6156 (8) | 0.4812 (5) | 0.1437 (4) | 0.0596 (16) | |
H35A | 0.6855 | 0.4543 | 0.1145 | 0.072* | |
C36 | 0.5819 (7) | 0.4687 (4) | 0.2133 (4) | 0.0514 (14) | |
H36A | 0.6313 | 0.4343 | 0.2316 | 0.062* | |
C41 | 0.4651 (6) | 0.0886 (4) | 0.3541 (3) | 0.0447 (12) | |
C42 | 0.5648 (6) | 0.0876 (4) | 0.2133 (3) | 0.0424 (12) | |
C43 | 0.5432 (7) | 0.2778 (4) | 0.4160 (4) | 0.0505 (14) | |
C44 | 0.7422 (6) | 0.1759 (3) | 0.3620 (3) | 0.0400 (12) | |
C45 | 0.6489 (7) | 0.2708 (4) | 0.2851 (3) | 0.0455 (13) | |
C46 | 0.3574 (7) | 0.1750 (4) | 0.2729 (3) | 0.0456 (13) | |
C51 | 0.337 (2) | 0.137 (2) | 0.8019 (18) | 0.136 (9)* | 0.50 |
H51A | 0.3515 | 0.0815 | 0.7983 | 0.163* | 0.50 |
C52 | 0.082 (4) | 0.067 (3) | 0.785 (2) | 0.171 (12)* | 0.50 |
H52A | 0.1080 | 0.0102 | 0.7757 | 0.257* | 0.50 |
H52B | 0.0338 | 0.0633 | 0.7343 | 0.257* | 0.50 |
H52C | 0.0141 | 0.0768 | 0.8249 | 0.257* | 0.50 |
C53 | 0.156 (4) | 0.216 (2) | 0.853 (2) | 0.153 (10)* | 0.50 |
H53A | 0.0925 | 0.2127 | 0.8930 | 0.230* | 0.50 |
H53B | 0.1056 | 0.2309 | 0.8132 | 0.230* | 0.50 |
H53C | 0.2474 | 0.2619 | 0.8805 | 0.230* | 0.50 |
N | 0.189 (2) | 0.1269 (15) | 0.8107 (13) | 0.119 (6)* | 0.50 |
O | 0.470 (3) | 0.1768 (16) | 0.7955 (15) | 0.172 (8)* | 0.50 |
O1 | 0.1361 (11) | 0.1425 (12) | 0.4438 (7) | 0.110 (5) | 0.50 |
H1 | 0.1045 | 0.1008 | 0.4226 | 0.132* | 0.50 |
H2 | 0.1547 | 0.1846 | 0.4515 | 0.132* | 0.50 |
O2 | 0.9342 (6) | 0.1380 (5) | 0.1697 (3) | 0.0900 (17) | |
H4 | 0.9600 | 0.1256 | 0.1162 | 0.108* | |
H3 | 0.9934 | 0.1143 | 0.1985 | 0.108* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0439 (4) | 0.0334 (4) | 0.0288 (3) | 0.0139 (3) | 0.0061 (3) | 0.0097 (3) |
Cu1 | 0.0349 (5) | 0.0379 (5) | 0.0517 (6) | 0.0048 (4) | 0.0045 (4) | 0.0104 (4) |
Cu2 | 0.0453 (5) | 0.0307 (5) | 0.0519 (6) | 0.0129 (4) | 0.0127 (4) | 0.0083 (4) |
Cu3 | 0.0362 (5) | 0.0497 (5) | 0.0269 (4) | 0.0045 (4) | 0.0022 (3) | 0.0091 (4) |
N1 | 0.041 (2) | 0.041 (3) | 0.047 (2) | 0.0054 (19) | 0.0039 (19) | 0.021 (2) |
N2 | 0.042 (2) | 0.039 (2) | 0.045 (2) | 0.0076 (19) | 0.0020 (19) | 0.015 (2) |
N3 | 0.046 (2) | 0.036 (2) | 0.039 (2) | 0.0140 (19) | 0.0096 (19) | 0.0077 (19) |
N4 | 0.051 (3) | 0.035 (2) | 0.045 (2) | 0.013 (2) | 0.008 (2) | 0.0086 (19) |
N5 | 0.038 (2) | 0.042 (2) | 0.040 (2) | 0.0051 (19) | 0.0024 (19) | 0.014 (2) |
N6 | 0.045 (2) | 0.045 (3) | 0.040 (2) | 0.004 (2) | 0.0037 (19) | 0.017 (2) |
N41 | 0.065 (3) | 0.068 (4) | 0.061 (3) | 0.003 (3) | 0.006 (3) | 0.039 (3) |
N42 | 0.093 (4) | 0.054 (3) | 0.033 (3) | 0.030 (3) | 0.010 (3) | 0.007 (2) |
N43 | 0.071 (4) | 0.061 (3) | 0.046 (3) | 0.020 (3) | 0.000 (3) | −0.003 (3) |
N44 | 0.051 (3) | 0.061 (3) | 0.085 (4) | 0.016 (2) | 0.004 (3) | 0.042 (3) |
N45 | 0.070 (4) | 0.072 (4) | 0.088 (4) | 0.011 (3) | 0.002 (3) | 0.054 (4) |
N46 | 0.054 (3) | 0.080 (4) | 0.071 (4) | 0.023 (3) | −0.006 (3) | 0.025 (3) |
C1 | 0.038 (3) | 0.046 (3) | 0.067 (4) | 0.002 (2) | 0.002 (3) | 0.022 (3) |
C2 | 0.041 (3) | 0.051 (3) | 0.071 (4) | 0.012 (3) | 0.016 (3) | 0.019 (3) |
C3 | 0.042 (3) | 0.050 (3) | 0.042 (3) | 0.010 (2) | 0.007 (2) | 0.016 (3) |
C4 | 0.057 (4) | 0.063 (4) | 0.081 (5) | 0.022 (3) | 0.021 (3) | 0.018 (4) |
C5 | 0.053 (4) | 0.041 (3) | 0.068 (4) | 0.011 (3) | 0.010 (3) | 0.007 (3) |
C6 | 0.046 (3) | 0.049 (3) | 0.044 (3) | 0.000 (2) | 0.003 (2) | 0.013 (3) |
C7 | 0.047 (3) | 0.045 (3) | 0.046 (3) | 0.001 (2) | 0.004 (2) | 0.006 (3) |
C8 | 0.062 (4) | 0.070 (4) | 0.052 (4) | 0.004 (3) | −0.008 (3) | 0.019 (3) |
C9 | 0.062 (4) | 0.079 (5) | 0.056 (4) | −0.008 (4) | −0.011 (3) | 0.011 (4) |
C10 | 0.052 (4) | 0.057 (4) | 0.065 (4) | −0.009 (3) | 0.010 (3) | −0.003 (3) |
C11 | 0.062 (4) | 0.052 (4) | 0.074 (5) | 0.006 (3) | 0.026 (3) | 0.022 (3) |
C12 | 0.052 (3) | 0.054 (3) | 0.047 (3) | 0.004 (3) | 0.010 (3) | 0.012 (3) |
C13 | 0.045 (3) | 0.054 (4) | 0.074 (4) | 0.011 (3) | 0.015 (3) | 0.024 (3) |
C14 | 0.042 (3) | 0.048 (3) | 0.075 (4) | 0.015 (3) | 0.006 (3) | 0.009 (3) |
C15 | 0.056 (3) | 0.045 (3) | 0.038 (3) | 0.024 (3) | 0.009 (2) | 0.015 (2) |
C16 | 0.078 (5) | 0.055 (4) | 0.082 (5) | 0.037 (3) | 0.023 (4) | 0.026 (4) |
C17 | 0.062 (4) | 0.037 (3) | 0.063 (4) | 0.015 (3) | 0.016 (3) | 0.010 (3) |
C18 | 0.056 (3) | 0.047 (3) | 0.061 (4) | 0.017 (3) | 0.009 (3) | 0.022 (3) |
C19 | 0.054 (3) | 0.036 (3) | 0.068 (4) | 0.013 (2) | 0.012 (3) | 0.020 (3) |
C20 | 0.101 (6) | 0.063 (4) | 0.070 (5) | 0.002 (4) | 0.003 (4) | 0.030 (4) |
C21 | 0.141 (9) | 0.074 (6) | 0.089 (6) | 0.001 (6) | 0.028 (6) | 0.044 (5) |
C22 | 0.091 (6) | 0.054 (4) | 0.096 (6) | −0.009 (4) | 0.018 (5) | 0.024 (4) |
C23 | 0.067 (4) | 0.048 (4) | 0.089 (5) | 0.004 (3) | −0.007 (4) | 0.019 (4) |
C24 | 0.070 (4) | 0.059 (4) | 0.081 (5) | 0.006 (3) | 0.002 (4) | 0.038 (4) |
C25 | 0.043 (3) | 0.072 (4) | 0.039 (3) | 0.001 (3) | 0.007 (2) | 0.014 (3) |
C26 | 0.038 (3) | 0.086 (5) | 0.043 (3) | −0.001 (3) | 0.005 (2) | 0.023 (3) |
C27 | 0.048 (3) | 0.035 (3) | 0.039 (3) | 0.003 (2) | −0.002 (2) | 0.013 (2) |
C28 | 0.056 (4) | 0.069 (4) | 0.056 (4) | −0.014 (3) | −0.012 (3) | 0.029 (3) |
C29 | 0.059 (4) | 0.048 (3) | 0.037 (3) | −0.003 (3) | −0.006 (3) | 0.017 (2) |
C30 | 0.046 (3) | 0.052 (3) | 0.036 (3) | 0.011 (2) | 0.005 (2) | 0.015 (2) |
C31 | 0.050 (3) | 0.042 (3) | 0.030 (3) | 0.007 (2) | 0.004 (2) | 0.009 (2) |
C32 | 0.070 (4) | 0.050 (3) | 0.057 (4) | 0.019 (3) | 0.005 (3) | 0.018 (3) |
C33 | 0.104 (6) | 0.065 (4) | 0.077 (5) | 0.018 (4) | 0.005 (4) | 0.048 (4) |
C34 | 0.093 (5) | 0.080 (5) | 0.043 (3) | 0.007 (4) | 0.010 (3) | 0.033 (3) |
C35 | 0.074 (4) | 0.062 (4) | 0.037 (3) | 0.012 (3) | 0.013 (3) | 0.016 (3) |
C36 | 0.060 (4) | 0.056 (3) | 0.044 (3) | 0.021 (3) | 0.011 (3) | 0.022 (3) |
C41 | 0.049 (3) | 0.047 (3) | 0.035 (3) | 0.011 (2) | 0.004 (2) | 0.016 (2) |
C42 | 0.055 (3) | 0.044 (3) | 0.033 (3) | 0.023 (2) | 0.009 (2) | 0.016 (2) |
C43 | 0.054 (3) | 0.050 (3) | 0.038 (3) | 0.020 (3) | 0.005 (2) | 0.006 (3) |
C44 | 0.051 (3) | 0.035 (3) | 0.040 (3) | 0.013 (2) | 0.008 (2) | 0.020 (2) |
C45 | 0.056 (3) | 0.044 (3) | 0.044 (3) | 0.021 (3) | 0.006 (2) | 0.022 (3) |
C46 | 0.055 (4) | 0.037 (3) | 0.042 (3) | 0.019 (2) | 0.006 (3) | 0.010 (2) |
O1 | 0.048 (5) | 0.207 (15) | 0.076 (7) | 0.061 (7) | 0.013 (5) | 0.066 (8) |
O2 | 0.075 (3) | 0.116 (5) | 0.070 (3) | 0.019 (3) | −0.003 (3) | 0.034 (3) |
Co—C41 | 1.893 (6) | C13—N4ii | 1.476 (8) |
Co—C44 | 1.893 (6) | C13—C14 | 1.478 (10) |
Co—C43 | 1.896 (6) | C13—H13A | 0.9700 |
Co—C42 | 1.896 (5) | C13—H13B | 0.9700 |
Co—C45 | 1.898 (6) | C14—H14A | 0.9700 |
Co—C46 | 1.907 (6) | C14—H14B | 0.9700 |
Cu1—N1i | 2.000 (5) | C15—C17 | 1.491 (9) |
Cu1—N1 | 2.000 (5) | C15—C16 | 1.504 (8) |
Cu1—N2i | 2.011 (4) | C16—H16A | 0.9600 |
Cu1—N2 | 2.011 (4) | C16—H16B | 0.9600 |
Cu1—N41 | 2.553 (5) | C16—H16C | 0.9600 |
Cu2—N3ii | 1.987 (4) | C17—C18 | 1.512 (9) |
Cu2—N3 | 1.987 (4) | C17—H17A | 0.9700 |
Cu2—N4ii | 2.012 (5) | C17—H17B | 0.9700 |
Cu2—N4 | 2.012 (5) | C18—C19 | 1.520 (9) |
Cu2—N42 | 2.511 (5) | C18—H18A | 0.9800 |
Cu3—N5iii | 1.982 (4) | C19—C20 | 1.352 (10) |
Cu3—N5 | 1.982 (4) | C19—C24 | 1.383 (10) |
Cu3—N6iii | 2.037 (4) | C20—C21 | 1.374 (12) |
Cu3—N6 | 2.037 (4) | C20—H20A | 0.9300 |
Cu3—N43 | 2.537 (6) | C21—C22 | 1.357 (14) |
N1—C3 | 1.263 (7) | C21—H21A | 0.9300 |
N1—C2 | 1.466 (7) | C22—C23 | 1.348 (12) |
N2—C6 | 1.468 (7) | C22—H22A | 0.9300 |
N2—C1i | 1.476 (8) | C23—C24 | 1.385 (10) |
N2—H2C | 0.9100 | C23—H23A | 0.9300 |
N3—C15 | 1.281 (7) | C24—H24A | 0.9300 |
N3—C14 | 1.461 (8) | C25—N6iii | 1.459 (7) |
N4—C18 | 1.460 (8) | C25—C26 | 1.479 (9) |
N4—C13ii | 1.476 (8) | C25—H25A | 0.9700 |
N4—H4D | 0.9100 | C25—H25B | 0.9700 |
N5—C27 | 1.277 (7) | C26—H26A | 0.9700 |
N5—C26 | 1.468 (7) | C26—H26B | 0.9700 |
N6—C25iii | 1.459 (7) | C27—C28 | 1.493 (8) |
N6—C30 | 1.472 (7) | C27—C29 | 1.504 (8) |
N6—H6B | 0.9100 | C28—H28A | 0.9600 |
N41—C41 | 1.149 (8) | C28—H28B | 0.9600 |
N42—C42 | 1.135 (7) | C28—H28C | 0.9600 |
N43—C43 | 1.144 (8) | C29—C30 | 1.514 (8) |
N44—C44 | 1.148 (7) | C29—H29A | 0.9700 |
N45—C45 | 1.139 (8) | C29—H29B | 0.9700 |
N46—C46 | 1.137 (8) | C30—C31 | 1.513 (8) |
C1—N2i | 1.476 (8) | C30—H30A | 0.9800 |
C1—C2 | 1.499 (9) | C31—C32 | 1.381 (9) |
C1—H1A | 0.9700 | C31—C36 | 1.386 (8) |
C1—H1B | 0.9700 | C32—C33 | 1.381 (10) |
C2—H2A | 0.9700 | C32—H32A | 0.9300 |
C2—H2B | 0.9700 | C33—C34 | 1.376 (12) |
C3—C5 | 1.498 (8) | C33—H33A | 0.9300 |
C3—C4 | 1.503 (9) | C34—C35 | 1.366 (11) |
C4—H4A | 0.9600 | C34—H34A | 0.9300 |
C4—H4B | 0.9600 | C35—C36 | 1.377 (9) |
C4—H4C | 0.9600 | C35—H35A | 0.9300 |
C5—C6 | 1.520 (9) | C36—H36A | 0.9300 |
C5—H5A | 0.9700 | C51—O | 1.298 (17) |
C5—H5B | 0.9700 | C51—N | 1.373 (17) |
C6—C7 | 1.524 (8) | C51—H51A | 0.9300 |
C6—H6A | 0.9800 | C52—N | 1.17 (4) |
C7—C8 | 1.384 (9) | C52—H52A | 0.9600 |
C7—C12 | 1.393 (9) | C52—H52B | 0.9600 |
C8—C9 | 1.395 (10) | C52—H52C | 0.9600 |
C8—H8A | 0.9300 | C53—N | 1.47 (3) |
C9—C10 | 1.349 (12) | C53—H53A | 0.9600 |
C9—H9A | 0.9300 | C53—H53B | 0.9600 |
C10—C11 | 1.362 (11) | C53—H53C | 0.9600 |
C10—H10A | 0.9300 | O1—H1 | 0.7704 |
C11—C12 | 1.386 (9) | O2—H22C | 0.9611 |
C11—H11A | 0.9300 | O2—H22D | 0.9705 |
C12—H12A | 0.9300 | ||
C41—Co—C44 | 88.0 (2) | N4ii—C13—H13A | 109.7 |
C41—Co—C43 | 93.8 (3) | C14—C13—H13A | 109.7 |
C44—Co—C43 | 91.4 (2) | N4ii—C13—H13B | 109.7 |
C41—Co—C42 | 91.8 (2) | C14—C13—H13B | 109.7 |
C44—Co—C42 | 90.6 (2) | H13A—C13—H13B | 108.2 |
C43—Co—C42 | 174.0 (3) | N3—C14—C13 | 110.0 (5) |
C41—Co—C45 | 177.0 (2) | N3—C14—H14A | 109.7 |
C44—Co—C45 | 89.4 (2) | C13—C14—H14A | 109.7 |
C43—Co—C45 | 84.6 (3) | N3—C14—H14B | 109.7 |
C42—Co—C45 | 89.8 (2) | C13—C14—H14B | 109.7 |
C41—Co—C46 | 89.0 (2) | H14A—C14—H14B | 108.2 |
C44—Co—C46 | 177.0 (2) | N3—C15—C17 | 120.5 (5) |
C43—Co—C46 | 89.5 (2) | N3—C15—C16 | 124.2 (6) |
C42—Co—C46 | 88.8 (2) | C17—C15—C16 | 115.3 (5) |
C45—Co—C46 | 93.6 (2) | C15—C16—H16A | 109.5 |
N1i—Cu1—N1 | 180.0 (3) | C15—C16—H16B | 109.5 |
N1i—Cu1—N2i | 95.05 (18) | H16A—C16—H16B | 109.5 |
N1—Cu1—N2i | 84.95 (18) | C15—C16—H16C | 109.5 |
N1i—Cu1—N2 | 84.95 (18) | H16A—C16—H16C | 109.5 |
N1—Cu1—N2 | 95.05 (18) | H16B—C16—H16C | 109.5 |
N2i—Cu1—N2 | 180.0 (3) | C15—C17—C18 | 121.3 (5) |
N1i—Cu1—N41 | 92.38 (19) | C15—C17—H17A | 107.0 |
N1—Cu1—N41 | 87.62 (19) | C18—C17—H17A | 107.0 |
N2i—Cu1—N41 | 92.98 (18) | C15—C17—H17B | 107.0 |
N2—Cu1—N41 | 87.02 (18) | C18—C17—H17B | 107.0 |
N3ii—Cu2—N3 | 180.0 (2) | H17A—C17—H17B | 106.7 |
N3ii—Cu2—N4ii | 95.11 (18) | N4—C18—C17 | 112.9 (5) |
N3—Cu2—N4ii | 84.89 (18) | N4—C18—C19 | 114.9 (5) |
N3ii—Cu2—N4 | 84.89 (18) | C17—C18—C19 | 109.2 (5) |
N3—Cu2—N4 | 95.11 (18) | N4—C18—H18A | 106.4 |
N4ii—Cu2—N4 | 180.0 (3) | C17—C18—H18A | 106.4 |
N3ii—Cu2—N42 | 90.30 (18) | C19—C18—H18A | 106.4 |
N3—Cu2—N42 | 89.70 (18) | C20—C19—C24 | 118.8 (6) |
N4ii—Cu2—N42 | 92.7 (2) | C20—C19—C18 | 119.1 (6) |
N4—Cu2—N42 | 87.3 (2) | C24—C19—C18 | 121.8 (6) |
N5iii—Cu3—N5 | 180.000 (1) | C19—C20—C21 | 120.4 (8) |
N5iii—Cu3—N6iii | 94.72 (18) | C19—C20—H20A | 119.8 |
N5—Cu3—N6iii | 85.28 (18) | C21—C20—H20A | 119.8 |
N5iii—Cu3—N6 | 85.28 (18) | C22—C21—C20 | 120.8 (9) |
N5—Cu3—N6 | 94.72 (18) | C22—C21—H21A | 119.6 |
N6iii—Cu3—N6 | 180.000 (1) | C20—C21—H21A | 119.6 |
N5iii—Cu3—N43 | 94.00 (19) | C23—C22—C21 | 119.7 (8) |
N5—Cu3—N43 | 86.00 (19) | C23—C22—H22A | 120.1 |
N6iii—Cu3—N43 | 86.6 (2) | C21—C22—H22A | 120.1 |
N6—Cu3—N43 | 93.4 (2) | C22—C23—C24 | 120.0 (8) |
C3—N1—C2 | 121.0 (5) | C22—C23—H23A | 120.0 |
C3—N1—Cu1 | 128.3 (4) | C24—C23—H23A | 120.0 |
C2—N1—Cu1 | 110.7 (3) | C19—C24—C23 | 120.1 (7) |
C6—N2—C1i | 114.4 (5) | C19—C24—H24A | 119.9 |
C6—N2—Cu1 | 113.3 (3) | C23—C24—H24A | 119.9 |
C1i—N2—Cu1 | 105.5 (3) | N6iii—C25—C26 | 110.6 (6) |
C6—N2—H2C | 107.8 | N6iii—C25—H25A | 109.5 |
C1i—N2—H2C | 107.8 | C26—C25—H25A | 109.5 |
Cu1—N2—H2C | 107.8 | N6iii—C25—H25B | 109.5 |
C15—N3—C14 | 120.1 (5) | C26—C25—H25B | 109.5 |
C15—N3—Cu2 | 128.9 (4) | H25A—C25—H25B | 108.1 |
C14—N3—Cu2 | 110.9 (3) | N5—C26—C25 | 109.4 (5) |
C18—N4—C13ii | 115.4 (5) | N5—C26—H26A | 109.8 |
C18—N4—Cu2 | 115.6 (4) | C25—C26—H26A | 109.8 |
C13ii—N4—Cu2 | 106.0 (3) | N5—C26—H26B | 109.8 |
C18—N4—H4D | 106.4 | C25—C26—H26B | 109.8 |
C13ii—N4—H4D | 106.4 | H26A—C26—H26B | 108.2 |
Cu2—N4—H4D | 106.4 | N5—C27—C28 | 124.1 (5) |
C27—N5—C26 | 121.0 (5) | N5—C27—C29 | 121.4 (5) |
C27—N5—Cu3 | 128.7 (4) | C28—C27—C29 | 114.4 (5) |
C26—N5—Cu3 | 110.3 (3) | C27—C28—H28A | 109.5 |
C25iii—N6—C30 | 116.9 (5) | C27—C28—H28B | 109.5 |
C25iii—N6—Cu3 | 104.5 (3) | H28A—C28—H28B | 109.5 |
C30—N6—Cu3 | 113.8 (3) | C27—C28—H28C | 109.5 |
C25iii—N6—H6B | 107.0 | H28A—C28—H28C | 109.5 |
C30—N6—H6B | 107.0 | H28B—C28—H28C | 109.5 |
Cu3—N6—H6B | 107.0 | C27—C29—C30 | 118.3 (5) |
C41—N41—Cu1 | 135.2 (5) | C27—C29—H29A | 107.7 |
C42—N42—Cu2 | 139.3 (5) | C30—C29—H29A | 107.7 |
C43—N43—Cu3 | 138.8 (5) | C27—C29—H29B | 107.7 |
N2i—C1—C2 | 109.2 (5) | C30—C29—H29B | 107.7 |
N2i—C1—H1A | 109.8 | H29A—C29—H29B | 107.1 |
C2—C1—H1A | 109.8 | N6—C30—C31 | 116.3 (5) |
N2i—C1—H1B | 109.8 | N6—C30—C29 | 111.4 (5) |
C2—C1—H1B | 109.8 | C31—C30—C29 | 110.1 (4) |
H1A—C1—H1B | 108.3 | N6—C30—H30A | 106.1 |
N1—C2—C1 | 109.2 (5) | C31—C30—H30A | 106.1 |
N1—C2—H2A | 109.8 | C29—C30—H30A | 106.1 |
C1—C2—H2A | 109.8 | C32—C31—C36 | 118.2 (5) |
N1—C2—H2B | 109.8 | C32—C31—C30 | 118.4 (5) |
C1—C2—H2B | 109.8 | C36—C31—C30 | 123.4 (5) |
H2A—C2—H2B | 108.3 | C33—C32—C31 | 121.2 (7) |
N1—C3—C5 | 121.2 (5) | C33—C32—H32A | 119.4 |
N1—C3—C4 | 125.4 (5) | C31—C32—H32A | 119.4 |
C5—C3—C4 | 113.5 (5) | C34—C33—C32 | 119.1 (7) |
C3—C4—H4A | 109.5 | C34—C33—H33A | 120.4 |
C3—C4—H4B | 109.5 | C32—C33—H33A | 120.4 |
H4A—C4—H4B | 109.5 | C35—C34—C33 | 120.8 (6) |
C3—C4—H4C | 109.5 | C35—C34—H34A | 119.6 |
H4A—C4—H4C | 109.5 | C33—C34—H34A | 119.6 |
H4B—C4—H4C | 109.5 | C34—C35—C36 | 119.6 (7) |
C3—C5—C6 | 118.4 (5) | C34—C35—H35A | 120.2 |
C3—C5—H5A | 107.7 | C36—C35—H35A | 120.2 |
C6—C5—H5A | 107.7 | C35—C36—C31 | 121.0 (6) |
C3—C5—H5B | 107.7 | C35—C36—H36A | 119.5 |
C6—C5—H5B | 107.7 | C31—C36—H36A | 119.5 |
H5A—C5—H5B | 107.1 | N41—C41—Co | 176.7 (5) |
N2—C6—C5 | 111.3 (5) | N42—C42—Co | 178.0 (5) |
N2—C6—C7 | 113.6 (5) | N43—C43—Co | 172.9 (6) |
C5—C6—C7 | 108.4 (5) | N44—C44—Co | 179.8 (7) |
N2—C6—H6A | 107.8 | N45—C45—Co | 174.4 (6) |
C5—C6—H6A | 107.8 | N46—C46—Co | 178.3 (6) |
C7—C6—H6A | 107.8 | O—C51—N | 158 (3) |
C8—C7—C12 | 118.5 (6) | O—C51—H51A | 101.0 |
C8—C7—C6 | 120.2 (6) | N—C51—H51A | 101.0 |
C12—C7—C6 | 121.0 (5) | N—C52—H52A | 109.5 |
C7—C8—C9 | 119.7 (7) | N—C52—H52B | 109.5 |
C7—C8—H8A | 120.1 | H52A—C52—H52B | 109.5 |
C9—C8—H8A | 120.1 | N—C52—H52C | 109.5 |
C10—C9—C8 | 121.0 (7) | H52A—C52—H52C | 109.5 |
C10—C9—H9A | 119.5 | H52B—C52—H52C | 109.5 |
C8—C9—H9A | 119.5 | N—C53—H53A | 109.5 |
C9—C10—C11 | 120.0 (6) | N—C53—H53B | 109.5 |
C9—C10—H10A | 120.0 | H53A—C53—H53B | 109.5 |
C11—C10—H10A | 120.0 | N—C53—H53C | 109.5 |
C10—C11—C12 | 120.5 (7) | H53A—C53—H53C | 109.5 |
C10—C11—H11A | 119.8 | H53B—C53—H53C | 109.5 |
C12—C11—H11A | 119.8 | C52—N—C51 | 135 (3) |
C11—C12—C7 | 120.1 (6) | C52—N—C53 | 113 (3) |
C11—C12—H12A | 119.9 | C51—N—C53 | 111 (2) |
C7—C12—H12A | 119.9 | H22C—O2—H22D | 108.5 |
N4ii—C13—C14 | 109.8 (5) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z; (iii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4D···O2 | 0.91 | 2.47 | 3.281 (7) | 149 |
N6—H6B···N45 | 0.91 | 2.51 | 3.380 (9) | 161 |
O2—H22D···N46iv | 0.97 | 2.24 | 2.912 (8) | 125 |
Symmetry code: (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu3Co2(CN)6(C26H32N6)3]·C3H7NO·3H2O |
Mr | 1877.47 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.2510 (3), 16.4054 (5), 17.8005 (5) |
α, β, γ (°) | 113.016 (1), 93.684 (1), 101.966 (1) |
V (Å3) | 2400.55 (13) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.05 |
Crystal size (mm) | 0.56 × 0.42 × 0.26 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.590, 0.772 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12146, 8189, 6842 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.200, 1.09 |
No. of reflections | 8189 |
No. of parameters | 557 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.10, −0.76 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Co—C41 | 1.893 (6) | Cu1—N41 | 2.553 (5) |
Co—C44 | 1.893 (6) | Cu2—N3 | 1.987 (4) |
Co—C43 | 1.896 (6) | Cu2—N4 | 2.012 (5) |
Co—C42 | 1.896 (5) | Cu2—N42 | 2.511 (5) |
Co—C45 | 1.898 (6) | Cu3—N5 | 1.982 (4) |
Co—C46 | 1.907 (6) | Cu3—N6 | 2.037 (4) |
Cu1—N1 | 2.000 (5) | Cu3—N43 | 2.537 (6) |
Cu1—N2 | 2.011 (4) | ||
C41—N41—Cu1 | 135.2 (5) | N43—C43—Co | 172.9 (6) |
C42—N42—Cu2 | 139.3 (5) | N44—C44—Co | 179.8 (7) |
C43—N43—Cu3 | 138.8 (5) | N45—C45—Co | 174.4 (6) |
N41—C41—Co | 176.7 (5) | N46—C46—Co | 178.3 (6) |
N42—C42—Co | 178.0 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4D···O2 | 0.91 | 2.47 | 3.281 (7) | 149 |
N6—H6B···N45 | 0.91 | 2.51 | 3.380 (9) | 161 |
O2—H22D···N46i | 0.97 | 2.24 | 2.912 (8) | 125 |
Symmetry code: (i) x+1, y, z. |
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For many years, chemists have devoted their efforts to assembling compounds by connecting building units to give supramolecular structures. Successful recent examples of this process are the cyano-bridged complexes (Misayaka et al., 1998, Re et al., 1998, Fujita et al., 1998, Ohba et al., 1999, Ohba et al., 1997) in which a cyanometallate anion serves as the bridging moiety to build a multidimensional structure with a second coordination center. When the cyanometallate building block is paramagnetic, molecular-based magnetic materials can be formed, and these have attracted considerable interest. A few high-temperature molecular magnets based on cyanide building blocks have been reported (Gadet et al., 1992, Entley et al., 1995, Mallah et al., 1993). The work of these authors shows that transition metal cyanides are good candidates for a system of molecule-based magnetic materials. However, the use of [Co(CN)6]3− as the bridging moiety in a multidimensional structure has never been reported. We have designed and synthesized a novel coordination polymer, {(CuL)3[Co(CN)6]2·DMF·3H2O}n, (I), and its structure is reported here.
Details of the molecular geometry are given in Table 1 and the asymmetric unit is shown in Fig.1. The title crystal structure consists of a neutral stair-shaped-layer network with the stoichiometry [CuL]3[Co(CN)6]2, together with water and DMF molecules. Unlike some complexes (Ferlay et al., 1996, Colacio et al., 1999, Kou et al., 1999), in which three [Ni(cyclam)] (cyclam is 1,4,8,11-tetraazacyclotetradecane) or [NiL] (L is 3,10-dimethyl-1,3,5,8,10,12-hexaazacyclotetradecane) groups connect three cyanide groups in a fac arrangement at an iron(III) or chromium(III) cation, in the title complex, each [Co(CN)6]3− unit uses three cyanide groups in a meridional arrangement to connect three [CuL]2+ units at the trans positions, and this particular local molecular disposition leads to a two-dimensional honeycomb network structure (Fig. 2a and Fig. 2b). This disposition is similar to that of {(NiL)3[Fe(CN)6]2.12H2O}n (L is 3,10-diethyl-1,3,5,8,10,12-hexaazacyclotetradecane; Kou, et al., 2000), but this compound has a brick-wall-like structure. The existance of a different structure with the same molecular disposition may be the result of the steric hindrance of the macrocycle ligands with the benzene groups in the title complex. The distances between adjacent Co and Cu atoms are 5.141 (2) Å for Co···Cu1, 5.179 (2) Å for Co···Cu2 and 5.150 (2) Å for Co···Cu3. Each CuL unit is linked to two hexacyanocobalt(III) ions. The coordination environment around the CuII ion in (CuL)2+ is an elongated octahedron, with short bonds formed by four N atoms from the ligand L [Cu—N = 1.982 (4)–2.037 (4) Å], The axial coordination sites are occupied by two N atoms from the cyanide group [Cu—N = 2.511 (5) and 2.553 (5) Å]. The CuII ion lies at the center of the elongated octahedron. The Cu—N distances are similar to those found in {[Cu(cyclam)]3[Cr(CN)6]2·4H2O}n [Cu—Ncyclam = 1.981 (8)–2.012 (8) Å and Cu—NCN = 2.474 (9)–2.638 (8) Å; cyclam is 1,4,8,11-tetraazacyclotetradecane; Salah El Fallah et al., 2003). The Co—C distances in (I) range from 1.893 (6) to 1.907 (6) Å. As expected, the Co—C—N bond angles vary only over a small range, 172.9 (6)–179.8 (7)°, whereas the corresponding Cu—N—C bond angles deviate significantly from linearity [Cu1—N41—C41 = 135.2 (5)°, Cu2—N42—C42 = 139.3 (5)° and Cu3—N43—C43 = 138.8 (5)°, respectively.
The structure is further stabilized by several hydrogen-bonding interactions (Table.2).