Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009490/sk1474sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009490/sk1474Isup2.hkl |
CCDC reference: 137008
Caution! Perchlorate salts are potentially explosive and should be handled in small quantities.
Ethylenediamine (en; 2 mmol) was added to an aqueous solution (20 ml) of Cu(ClO4)2·6H2O (1 mmol) with stirring. The colour of the solution turned to blue-violet. After stirring for 20 min, the solution was then mixed with an aqueous solution (20 ml) of K3[Co(CN)6] (1 mmol). The resulting solution was filtered and the filtrate was left for one week in the dark at room temperature. Violet-red crystals of {[Cu(en)2][KCo(CN)6]}n, (I), suitable for X-ray diffraction analysis, were obtained. The product is stable under ambient conditions, and is insoluble in most common inorganic and organic solvents. Analysis, found: C 27.14, H 3.58, N 31.32%; calculated for C10H16CoCuKN10: C 27.43, H 3.68, N 32.00%.
H atoms were treated as riding, with C—H = 0.97 and N—H = 0.90 Å, and with Uiso(H) equal to 1.2 times Ueq of the parent atom. Query.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Cu(C2H8N2)2][KCo(CN)6] | F(000) = 884 |
Mr = 437.90 | Dx = 1.764 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.391 (2) Å | Cell parameters from 26 reflections |
b = 16.866 (3) Å | θ = 3.0–17.5° |
c = 11.791 (2) Å | µ = 2.56 mm−1 |
β = 98.91 (2)° | T = 295 K |
V = 1648.6 (6) Å3 | Block, violet-red |
Z = 4 | 0.44 × 0.41 × 0.20 mm |
Siemens P4 diffractometer | 1606 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 27°, θmin = 2.4° |
ω scans | h = 0→10 |
Absorption correction: ψ-scan (North et al., 1968) | k = −1→21 |
Tmin = 0.333, Tmax = 0.599 | l = −15→14 |
2172 measured reflections | 3 standard reflections every 97 reflections |
1797 independent reflections | intensity decay: 3.6% |
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)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0355P)2 + 0.0854P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
1797 reflections | Δρmax = 0.43 e Å−3 |
127 parameters | Δρmin = −0.28 e Å−3 |
0 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: 0.0044 (3) |
[Cu(C2H8N2)2][KCo(CN)6] | V = 1648.6 (6) Å3 |
Mr = 437.90 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 8.391 (2) Å | µ = 2.56 mm−1 |
b = 16.866 (3) Å | T = 295 K |
c = 11.791 (2) Å | 0.44 × 0.41 × 0.20 mm |
β = 98.91 (2)° |
Siemens P4 diffractometer | 1606 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.013 |
Tmin = 0.333, Tmax = 0.599 | 3 standard reflections every 97 reflections |
2172 measured reflections | intensity decay: 3.6% |
1797 independent reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.43 e Å−3 |
1797 reflections | Δρmin = −0.28 e Å−3 |
127 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) | |
Cu | 0 | 0 | 0 | 0.03702 (13) | |
Co | −1/2 | −0.11561 (2) | −1/4 | 0.01809 (11) | |
K | −1/2 | 0.14220 (4) | −1/4 | 0.02579 (14) | |
N1 | 0.1150 (2) | 0.08553 (11) | −0.07137 (15) | 0.0381 (5) | |
H1A | 0.2174 | 0.0898 | −0.0355 | 0.046* | 0.535 (4) |
H1B | 0.1164 | 0.0748 | −0.1460 | 0.046* | 0.535 (4) |
N2 | −0.1205 (2) | 0.08848 (12) | 0.05931 (17) | 0.0472 (6) | |
H2A | −0.2240 | 0.0876 | 0.0247 | 0.057* | 0.535 (4) |
H2B | −0.1192 | 0.0824 | 0.1353 | 0.057* | 0.535 (4) |
C1 | 0.0287 (10) | 0.1575 (5) | −0.0597 (9) | 0.055 (2) | 0.535 (4) |
H1C | 0.1037 | 0.2015 | −0.0559 | 0.066* | 0.535 (4) |
H1D | −0.0509 | 0.1647 | −0.1279 | 0.066* | 0.535 (4) |
C2 | −0.0510 (12) | 0.1605 (6) | 0.0384 (7) | 0.056 (2) | 0.535 (4) |
H2C | 0.0261 | 0.1754 | 0.1050 | 0.068* | 0.535 (4) |
H2D | −0.1341 | 0.2010 | 0.0268 | 0.068* | 0.535 (4) |
H1A' | 0.2219 | 0.0765 | −0.0563 | 0.046* | 0.465 (4) |
H1B' | 0.0853 | 0.0840 | −0.1480 | 0.046* | 0.465 (4) |
H2A' | −0.2265 | 0.0769 | 0.0496 | 0.057* | 0.465 (4) |
H2B' | −0.0861 | 0.0951 | 0.1349 | 0.057* | 0.465 (4) |
C1' | 0.0804 (10) | 0.1669 (7) | −0.0284 (9) | 0.044 (2) | 0.465 (4) |
H1'1 | 0.0912 | 0.2067 | −0.0860 | 0.053* | 0.465 (4) |
H1'2 | 0.1542 | 0.1795 | 0.0409 | 0.053* | 0.465 (4) |
C2' | −0.0944 (12) | 0.1636 (7) | −0.0039 (7) | 0.0413 (18) | 0.465 (4) |
H2'1 | −0.1154 | 0.2090 | 0.0420 | 0.050* | 0.465 (4) |
H2'2 | −0.1686 | 0.1655 | −0.0756 | 0.050* | 0.465 (4) |
N3 | −0.2401 (2) | −0.24183 (11) | −0.24466 (15) | 0.0451 (5) | |
N4 | −0.49330 (19) | −0.11768 (12) | 0.00952 (13) | 0.0366 (4) | |
N5 | −0.2312 (2) | 0.00773 (11) | −0.20865 (17) | 0.0384 (4) | |
C3 | −0.3384 (2) | −0.19515 (11) | −0.24350 (15) | 0.0267 (4) | |
C4 | −0.4945 (2) | −0.11660 (11) | −0.08784 (15) | 0.0241 (4) | |
C5 | −0.3349 (2) | −0.03750 (11) | −0.22782 (14) | 0.0234 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0317 (2) | 0.0334 (2) | 0.0518 (2) | 0.00252 (15) | 0.02479 (17) | 0.00547 (16) |
Co | 0.01755 (18) | 0.01938 (18) | 0.01787 (17) | 0 | 0.00438 (12) | 0 |
K | 0.0281 (3) | 0.0260 (3) | 0.0241 (3) | 0 | 0.0067 (2) | 0 |
N1 | 0.0324 (10) | 0.0466 (12) | 0.0372 (9) | −0.0069 (8) | 0.0115 (7) | 0.0009 (8) |
N2 | 0.0463 (12) | 0.0492 (13) | 0.0516 (12) | 0.0145 (10) | 0.0249 (9) | 0.0086 (10) |
C1 | 0.053 (5) | 0.030 (4) | 0.086 (6) | −0.005 (3) | 0.023 (4) | 0.014 (4) |
C2 | 0.066 (6) | 0.044 (4) | 0.063 (6) | −0.003 (4) | 0.022 (4) | −0.011 (5) |
C1' | 0.035 (5) | 0.039 (4) | 0.061 (5) | −0.018 (3) | 0.012 (3) | −0.007 (3) |
C2' | 0.047 (5) | 0.034 (3) | 0.043 (5) | 0.012 (3) | 0.008 (3) | 0.011 (4) |
N3 | 0.0456 (11) | 0.0461 (11) | 0.0437 (11) | 0.0194 (10) | 0.0077 (9) | −0.0019 (10) |
N4 | 0.0382 (10) | 0.0498 (12) | 0.0227 (9) | 0.0014 (8) | 0.0072 (7) | 0.0024 (7) |
N5 | 0.0351 (10) | 0.0367 (10) | 0.0448 (11) | −0.0108 (8) | 0.0112 (8) | −0.0062 (8) |
C3 | 0.0270 (9) | 0.0283 (10) | 0.0248 (9) | 0.0028 (8) | 0.0042 (7) | −0.0005 (8) |
C4 | 0.0200 (8) | 0.0262 (9) | 0.0262 (10) | 0.0020 (7) | 0.0042 (7) | 0.0004 (7) |
C5 | 0.0249 (9) | 0.0248 (9) | 0.0215 (8) | 0.0013 (8) | 0.0068 (7) | −0.0013 (7) |
Cu—N2i | 1.9895 (19) | N1—H1B | 0.9000 |
Cu—N2 | 1.9895 (19) | N2—C2 | 1.386 (11) |
Cu—N1 | 1.9928 (18) | N2—H2A | 0.9000 |
Cu—N1i | 1.9928 (18) | N2—H2B | 0.9000 |
Co—C5ii | 1.9001 (19) | C1—C2 | 1.424 (15) |
Co—C5 | 1.9001 (19) | C1—H1C | 0.9700 |
Co—C3 | 1.9004 (19) | C1—H1D | 0.9700 |
Co—C3ii | 1.9004 (19) | C2—H2C | 0.9700 |
Co—C4 | 1.9056 (18) | C2—H2D | 0.9700 |
Co—C4ii | 1.9056 (18) | C1'—C2' | 1.539 (15) |
K—N3iii | 2.8158 (18) | C1'—H1'1 | 0.9700 |
K—N3iv | 2.8158 (18) | C1'—H1'2 | 0.9700 |
K—N4v | 2.8746 (16) | C2'—H2'1 | 0.9700 |
K—N4vi | 2.8746 (16) | C2'—H2'2 | 0.9700 |
K—N5ii | 3.183 (2) | N3—C3 | 1.142 (2) |
K—N5 | 3.183 (2) | N3—Kvii | 2.8158 (18) |
K—C5 | 3.326 (2) | N4—C4 | 1.147 (2) |
K—C5ii | 3.326 (2) | N4—Kvi | 2.8746 (16) |
N1—C1 | 1.431 (10) | N5—C5 | 1.153 (2) |
N1—H1A | 0.9000 | ||
N2i—Cu—N2 | 180.00 (14) | C2—N2—Cu | 110.1 (4) |
N2i—Cu—N1 | 95.10 (9) | C2—N2—H2A | 109.6 |
N2—Cu—N1 | 84.90 (9) | Cu—N2—H2A | 109.6 |
N2i—Cu—N1i | 84.90 (9) | C2—N2—H2B | 109.6 |
N2—Cu—N1i | 95.10 (9) | Cu—N2—H2B | 109.6 |
N1—Cu—N1i | 180.00 (12) | H2A—N2—H2B | 108.1 |
C5ii—Co—C5 | 92.21 (11) | C2—C1—N1 | 114.6 (8) |
C5ii—Co—C3 | 174.44 (7) | C2—C1—H1C | 108.6 |
C5—Co—C3 | 89.05 (8) | N1—C1—H1C | 108.6 |
C5ii—Co—C3ii | 89.05 (8) | C2—C1—H1D | 108.6 |
C5—Co—C3ii | 174.44 (7) | N1—C1—H1D | 108.6 |
C3—Co—C3ii | 90.20 (12) | H1C—C1—H1D | 107.6 |
C5ii—Co—C4 | 92.74 (7) | N2—C2—C1 | 112.1 (7) |
C5—Co—C4 | 87.95 (7) | N2—C2—H2C | 109.2 |
C3—Co—C4 | 92.71 (8) | C1—C2—H2C | 109.2 |
C3ii—Co—C4 | 86.58 (8) | N2—C2—H2D | 109.2 |
C5ii—Co—C4ii | 87.95 (7) | C1—C2—H2D | 109.2 |
C5—Co—C4ii | 92.74 (7) | H2C—C2—H2D | 107.9 |
C3—Co—C4ii | 86.58 (8) | C2'—C1'—H1'1 | 110.6 |
C3ii—Co—C4ii | 92.71 (8) | C2'—C1'—H1'2 | 110.6 |
C4—Co—C4ii | 179.00 (11) | H1'1—C1'—H1'2 | 108.7 |
C1—N1—Cu | 106.8 (4) | C1'—C2'—H2'1 | 109.7 |
C1—N1—H1A | 110.4 | C1'—C2'—H2'2 | 109.7 |
Cu—N1—H1A | 110.4 | H2'1—C2'—H2'2 | 108.2 |
C1—N1—H1B | 110.4 | N3—C3—Co | 176.75 (18) |
Cu—N1—H1B | 110.4 | N4—C4—Co | 179.06 (18) |
H1A—N1—H1B | 108.6 | N5—C5—Co | 176.10 (17) |
N2i—Cu—N1—C1 | 169.2 (4) | Cu—N2—C2—C1 | 27.7 (9) |
N2—Cu—N1—C1 | −10.8 (4) | N1—C1—C2—N2 | −39.4 (11) |
N1—Cu—N2—C2 | −9.1 (4) | C3—Co—C5—K | 174.59 (7) |
N1i—Cu—N2—C2 | 170.9 (4) | C4—Co—C5—K | −92.67 (7) |
Cu—N1—C1—C2 | 29.7 (8) | C4ii—Co—C5—K | 88.06 (7) |
Symmetry codes: (i) −x, −y, −z; (ii) −x−1, y, −z−1/2; (iii) −x−1/2, y+1/2, −z−1/2; (iv) x−1/2, y+1/2, z; (v) x, −y, z−1/2; (vi) −x−1, −y, −z; (vii) x+1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H8N2)2][KCo(CN)6] |
Mr | 437.90 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 8.391 (2), 16.866 (3), 11.791 (2) |
β (°) | 98.91 (2) |
V (Å3) | 1648.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.56 |
Crystal size (mm) | 0.44 × 0.41 × 0.20 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.333, 0.599 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2172, 1797, 1606 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.062, 1.05 |
No. of reflections | 1797 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.28 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Sheldrick, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Cu—N2i | 1.9895 (19) | Co—C4ii | 1.9056 (18) |
Cu—N2 | 1.9895 (19) | K—N3iii | 2.8158 (18) |
Cu—N1 | 1.9928 (18) | K—N3iv | 2.8158 (18) |
Cu—N1i | 1.9928 (18) | K—N4v | 2.8746 (16) |
Co—C5ii | 1.9001 (19) | K—N4vi | 2.8746 (16) |
Co—C5 | 1.9001 (19) | K—N5ii | 3.183 (2) |
Co—C3 | 1.9004 (19) | K—N5 | 3.183 (2) |
Co—C3ii | 1.9004 (19) | K—C5 | 3.326 (2) |
Co—C4 | 1.9056 (18) | K—C5ii | 3.326 (2) |
N2i—Cu—N1i | 84.90 (9) | C3—Co—C4 | 92.71 (8) |
N2—Cu—N1i | 95.10 (9) | C3ii—Co—C4 | 86.58 (8) |
C5ii—Co—C5 | 92.21 (11) | C4—Co—C4ii | 179.00 (11) |
C5ii—Co—C3 | 174.44 (7) | N3—C3—Co | 176.75 (18) |
C5—Co—C3 | 89.05 (8) | N4—C4—Co | 179.06 (18) |
C3—Co—C3ii | 90.20 (12) | N5—C5—Co | 176.10 (17) |
C5—Co—C4 | 87.95 (7) |
Symmetry codes: (i) −x, −y, −z; (ii) −x−1, y, −z−1/2; (iii) −x−1/2, y+1/2, −z−1/2; (iv) x−1/2, y+1/2, z; (v) x, −y, z−1/2; (vi) −x−1, −y, −z. |
The design and synthesis of well characterized molecular-based magnets remains a challenge (Kahn, 1995). It is well known that hexacyanometallate ions, [M(CN)6]3-, acting as good building blocks, play an important role in realising bimetallic assemblies. Although a series of bimetallic assemblies derived from a hexacyanometallate ion and a four-coordinate bis(diamine)-metal complex have been synthesized (Ohba et al., 1994; Fukita et al., 1998; Yuan et al., 2000), the most commonly employed building blocks are [Fe(CN)6]3-, [Cr(CN)6]3- and [Co(CN)6]3- (Ferbinteanu et al., 1999). We have previously reported the three-dimensional porous framework complex {[Cu(en)2][KCr(CN)6]}n (Yuan et al., 2000), and we report here the crystal structure of the title complex, {[Cu(en)2][KCo(CN)6]}n, (I). \sch
The structure of (I) is shown in Fig. 1, 2 and 3. The Co3+ ion is coordinated by six C atoms of the cyanide groups to form a slightly distorted octahedral geometry, and the Co—C bond lengths are 1.9001 (19), 1.9004 (19) and 1.9056 (18) Å, which are similar to the values found in K3[Co(CN)6] [1.876 (11), 1.896 (11) and 1.916 (11) Å; Vannerberg, 1972] and less than the Cr—C bond lengths in the similar complex {[Cu(en)2][KCr(CN)6]}n [2.065 (3), 2.080 (2) and 2.085 (2) Å]. The C3—Co—C4, C4—Co—C5 and C5—Co—C3 bond angles are 92.71 (8), 87.95 (7) and 89.05 (8)°, respectively. The K+ cation is unusually coordinated by six cyanide groups of neighbouring cyanometallates, which act as bridging ligands to link the Co3+ and K+ ions.
All the cyanide groups in (I) can be divided into two groups according to the K···N distances and C—N···K angles. One is with a linear Co—C—N—K linkage, using the σ electrons of the N atom coordinating to the K+ cation, the K···N distances of which are 2.8158 (18) and 2.8746 (16) Å; the C—N···K angles are 179.28 (17) and 172.46 (17)°. The other is with a non-linear Co—C—N—K linkage, using the π electrons of the CN group coordinating to the K+ cation (Guo & Mak, 1998). Here, the K···N and K···C distances are 3.183 (2) and 3.326 (2) Å, respectively; the K···N distance is much longer than that of the above linear span. The C—N···K and N—C···K angles are 86.88 (14) and 72.85 (13)°, respectively.
The three-dimensional framework of (I) is composed of two kinds of linkage, CN—Co—CN—K and Co—CN—K—CN, with σ- and π-coordination forming a distorted cube-like void space, as shown in Fig. 2, with sides of about 9.0 × 8.9 Å. There are two small squares in both the upper and lower planes of the cube, which are composed of KOC, CoD and two CN with a π-coordination mode. Three other squares are as follows: KOD, CoE and two CN, KOG, CoF and two CN, and KOH, CoJ and two CN (atom labels as in Fig. 2). The sides of the square are about 3.2 × 3.1 Å. The complex [Cu(en)2]2+ ions occupy the centre of the cube with two positions of occupancies 0.535 and 0.465.
The Cu—N bond lengths within [Cu(en)2]2+ are 1.9929 (18) and 1.9895 (19) Å, which are similar to those found in [Cu(en)2X2] (where X is NCS-, BF4-, ClO4-, NO3- or Cl-, Br-; Procter et al., 1968). The distance between Cu and the nearest cyano N atom is 2.891 (4) Å. The Cu2+ ion is coordinated by four N atoms from two en ligands and two cyano N atoms, forming an elongated octahedron geometry.