
Acta Cryst. (2010). E66, m661-m662 [ doi:10.1107/S1600536810016995 ]
2-cyanido-dicyanidobis{2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}(1,4,8,11-tetraazacyclotetradecane)dichromium(III)nickel(II) methanol disolvateIn the title compound, [Cr2Ni(C16H14N2O2)2(CN)4(C10H24N4)]·2CH3OH, each [Cr(salen)(CN)2] unit {salen is 2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolate} acts as a monodentate ligand through one of its two cyanide groups N bound to a central [Ni(cyclam)]2+ core (cyclam is 1,4,8,11-tetraazacyclotetradecane). Each CrIII ion is coordinated by two N and two O atoms from a salen ligand situated in the equatorial plane with two trans cyanide C atoms, yielding a distorted octahedral coordination geometry. The NiII atom lies on an inversion center and is octahedrally coordinated by a cyclam ligand lying in the equatorial plane and by two cyanide N atoms. The asymmetric unit contains one half of the complex molecule and a methanol solvent molecule. In the crystal structure, the complex molecule is linked to the methanol solvent molecules via O-H
O and N-H
O hydrogen bonds. Individual complex molecules are linked by C-H
N hydrogen bonds, forming chains along b.
K[Cr(salen)(CN)2].H2O was synthesized according to the procedure described in the literature (Yamada et al., 1969). Ni(cyclam)(ClO4)2 was synthesized as described previously (Bosnich et al., (1965).
A solution of K[Cr(salen)(CN)2].H2O (79.6 mg, 0.2 mmol) in methanol (5 ml) was added dropwise to a solution of Ni(cyclam)(ClO4)2 (45.5 mg, 0.1 mmol) in water (3 ml). The mixture was stirred at room temperature for 5 min s and then filtered. Orange block crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of the filtrate.
Aromatic H atoms were placed in calculated positions with C—H = 0.93 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
| [Cr2Ni(C16H14N2O2)2(CN)4(C10H24N4)]·2CH4O | F(000) = 1112 |
| Mr = 1063.77 | Dx = 1.477 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 7889 reflections |
| a = 9.5711 (19) Å | θ = 2.2–27.9° |
| b = 18.936 (4) Å | µ = 0.90 mm−1 |
| c = 13.593 (3) Å | T = 100 K |
| β = 103.93 (3)° | Block, orange |
| V = 2391.1 (9) Å3 | 0.25 × 0.15 × 0.09 mm |
| Z = 2 |
| Bruker SMART CCD area-detector diffractometer | 5363 independent reflections |
| Radiation source: fine-focus sealed tube | 5077 reflections with I > 2σ(I) |
| graphite | Rint = 0.0000 |
| Detector resolution: 8.366 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
| φ and ω scans | h = 0→12 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = 0→24 |
| Tmin = 0.851, Tmax = 0.922 | l = −17→17 |
| 5363 measured reflections |
| 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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.132 | H-atom parameters constrained |
| S = 1.16 | w = 1/[σ2(Fo2) + (0.0531P)2 + 5.7746P] where P = (Fo2 + 2Fc2)/3 |
| 5363 reflections | (Δ/σ)max = 0.001 |
| 314 parameters | Δρmax = 0.76 e Å−3 |
| 0 restraints | Δρmin = −0.76 e Å−3 |
| [Cr2Ni(C16H14N2O2)2(CN)4(C10H24N4)]·2CH4O | V = 2391.1 (9) Å3 |
| Mr = 1063.77 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 9.5711 (19) Å | µ = 0.90 mm−1 |
| b = 18.936 (4) Å | T = 100 K |
| c = 13.593 (3) Å | 0.25 × 0.15 × 0.09 mm |
| β = 103.93 (3)° |
| Bruker SMART CCD area-detector diffractometer | 5363 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5077 reflections with I > 2σ(I) |
| Tmin = 0.851, Tmax = 0.922 | Rint = 0.0000 |
| 5363 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
| wR(F2) = 0.132 | Δρmax = 0.76 e Å−3 |
| S = 1.16 | Δρmin = −0.76 e Å−3 |
| 5363 reflections | Absolute structure: ? |
| 314 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
| O1 | 1.2639 (2) | 0.12757 (10) | 1.40979 (14) | 0.0198 (4) | |
| C1 | 1.3690 (3) | 0.10694 (14) | 1.4854 (2) | 0.0196 (5) | |
| C2 | 1.3393 (3) | 0.09542 (15) | 1.5811 (2) | 0.0238 (6) | |
| H1 | 1.2466 | 0.1031 | 1.5889 | 0.029* | |
| C3 | 1.4453 (4) | 0.07288 (16) | 1.6633 (2) | 0.0292 (6) | |
| H2 | 1.4231 | 0.0671 | 1.7258 | 0.035* | |
| C4 | 1.5836 (4) | 0.05875 (17) | 1.6546 (2) | 0.0302 (7) | |
| H3 | 1.6532 | 0.0424 | 1.7100 | 0.036* | |
| C5 | 1.6166 (3) | 0.06930 (15) | 1.5626 (2) | 0.0249 (6) | |
| H4 | 1.7095 | 0.0600 | 1.5563 | 0.030* | |
| C6 | 1.5121 (3) | 0.09400 (14) | 1.4777 (2) | 0.0205 (5) | |
| C7 | 1.5585 (3) | 0.10267 (15) | 1.3849 (2) | 0.0211 (5) | |
| H5 | 1.6503 | 0.0871 | 1.3840 | 0.025* | |
| N1 | 1.4815 (2) | 0.13043 (12) | 1.30349 (17) | 0.0181 (4) | |
| Cr1 | 1.28346 (4) | 0.17173 (2) | 1.28585 (3) | 0.01505 (12) | |
| C8 | 1.3751 (3) | 0.26188 (15) | 1.3624 (2) | 0.0211 (5) | |
| N2 | 1.4268 (3) | 0.31239 (15) | 1.4018 (2) | 0.0315 (6) | |
| C9 | 1.1978 (3) | 0.08685 (13) | 1.19052 (19) | 0.0150 (5) | |
| N3 | 1.1395 (3) | 0.05280 (14) | 1.1224 (2) | 0.0262 (5) | |
| O2 | 1.08976 (19) | 0.21092 (10) | 1.25226 (14) | 0.0174 (4) | |
| C10 | 1.0208 (3) | 0.23457 (13) | 1.1621 (2) | 0.0171 (5) | |
| C11 | 0.8713 (3) | 0.24589 (14) | 1.1438 (2) | 0.0201 (5) | |
| H6 | 0.8254 | 0.2372 | 1.1955 | 0.024* | |
| C12 | 0.7910 (3) | 0.26948 (15) | 1.0515 (2) | 0.0230 (6) | |
| H7 | 0.6924 | 0.2760 | 1.0420 | 0.028* | |
| C13 | 0.8559 (3) | 0.28365 (16) | 0.9720 (2) | 0.0263 (6) | |
| H8 | 0.8013 | 0.2989 | 0.9095 | 0.032* | |
| C14 | 1.0025 (3) | 0.27454 (15) | 0.9879 (2) | 0.0226 (5) | |
| H9 | 1.0469 | 0.2852 | 0.9359 | 0.027* | |
| C15 | 1.0869 (3) | 0.24956 (14) | 1.0807 (2) | 0.0183 (5) | |
| C16 | 1.2394 (3) | 0.24080 (14) | 1.0865 (2) | 0.0205 (5) | |
| H10 | 1.2736 | 0.2560 | 1.0316 | 0.025* | |
| N4 | 1.3299 (2) | 0.21365 (12) | 1.16162 (17) | 0.0179 (4) | |
| C17 | 1.4833 (3) | 0.20758 (16) | 1.1619 (2) | 0.0231 (6) | |
| H11 | 1.5374 | 0.2463 | 1.1997 | 0.028* | |
| H12 | 1.4956 | 0.2089 | 1.0932 | 0.028* | |
| C18 | 1.5359 (3) | 0.13719 (16) | 1.2118 (2) | 0.0222 (5) | |
| H13 | 1.5006 | 0.0986 | 1.1656 | 0.027* | |
| H14 | 1.6403 | 0.1358 | 1.2294 | 0.027* | |
| Ni1 | 1.0000 | 0.0000 | 1.0000 | 0.01755 (13) | |
| C19 | 1.2881 (3) | −0.00106 (16) | 0.9439 (2) | 0.0234 (6) | |
| H15 | 1.3293 | 0.0285 | 1.0019 | 0.028* | |
| H16 | 1.3413 | 0.0073 | 0.8926 | 0.028* | |
| N5 | 1.1361 (2) | 0.01852 (13) | 0.90325 (18) | 0.0207 (5) | |
| H17 | 1.1026 | −0.0078 | 0.8465 | 0.025* | |
| C20 | 1.1149 (3) | 0.09359 (15) | 0.8731 (2) | 0.0240 (6) | |
| H18 | 1.1485 | 0.1018 | 0.8122 | 0.029* | |
| H19 | 1.1698 | 0.1235 | 0.9265 | 0.029* | |
| C21 | 0.9557 (3) | 0.11151 (16) | 0.8536 (2) | 0.0250 (6) | |
| H20 | 0.9409 | 0.1611 | 0.8361 | 0.030* | |
| H21 | 0.9014 | 0.0837 | 0.7973 | 0.030* | |
| N6 | 0.9049 (3) | 0.09605 (13) | 0.94632 (17) | 0.0211 (5) | |
| H22 | 0.9418 | 0.1298 | 0.9931 | 0.025* | |
| C22 | 0.7465 (3) | 0.09755 (16) | 0.9297 (2) | 0.0239 (6) | |
| H23 | 0.7045 | 0.0646 | 0.8762 | 0.029* | |
| H24 | 0.7118 | 0.1444 | 0.9074 | 0.029* | |
| C23 | 0.6967 (3) | 0.07874 (16) | 1.0240 (2) | 0.0251 (6) | |
| H25 | 0.5962 | 0.0919 | 1.0131 | 0.030* | |
| H26 | 0.7507 | 0.1071 | 1.0797 | 0.030* | |
| C24 | 0.9633 (4) | 0.04217 (18) | 0.3659 (3) | 0.0322 (7) | |
| H27 | 1.0537 | 0.0235 | 0.3590 | 0.048* | |
| H28 | 0.8967 | 0.0041 | 0.3649 | 0.048* | |
| H29 | 0.9773 | 0.0672 | 0.4289 | 0.048* | |
| O3 | 0.9074 (2) | 0.08903 (12) | 0.28438 (17) | 0.0290 (5) | |
| H30 | 0.9666 | 0.1201 | 0.2830 | 0.044* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0190 (9) | 0.0243 (9) | 0.0166 (9) | 0.0000 (7) | 0.0051 (7) | −0.0010 (7) |
| C1 | 0.0251 (13) | 0.0169 (12) | 0.0168 (12) | −0.0006 (10) | 0.0047 (10) | −0.0012 (9) |
| C2 | 0.0291 (14) | 0.0225 (13) | 0.0217 (13) | −0.0005 (11) | 0.0098 (11) | −0.0008 (10) |
| C3 | 0.0450 (18) | 0.0252 (14) | 0.0165 (13) | −0.0004 (13) | 0.0057 (12) | 0.0009 (11) |
| C4 | 0.0352 (16) | 0.0289 (15) | 0.0213 (14) | −0.0003 (12) | −0.0035 (12) | 0.0014 (11) |
| C5 | 0.0224 (13) | 0.0236 (13) | 0.0252 (14) | −0.0003 (11) | −0.0009 (11) | 0.0004 (11) |
| C6 | 0.0221 (13) | 0.0190 (12) | 0.0187 (12) | −0.0047 (10) | 0.0018 (10) | −0.0033 (10) |
| C7 | 0.0165 (12) | 0.0234 (13) | 0.0233 (13) | 0.0001 (10) | 0.0047 (10) | −0.0046 (10) |
| N1 | 0.0161 (10) | 0.0236 (11) | 0.0163 (10) | −0.0017 (8) | 0.0073 (8) | −0.0038 (8) |
| Cr1 | 0.0139 (2) | 0.0187 (2) | 0.0133 (2) | −0.00180 (14) | 0.00477 (15) | −0.00241 (14) |
| C8 | 0.0179 (12) | 0.0277 (14) | 0.0182 (12) | −0.0023 (10) | 0.0055 (10) | −0.0047 (10) |
| N2 | 0.0283 (13) | 0.0338 (14) | 0.0339 (14) | −0.0063 (11) | 0.0102 (11) | −0.0067 (11) |
| C9 | 0.0132 (10) | 0.0153 (11) | 0.0165 (11) | −0.0002 (9) | 0.0035 (9) | −0.0035 (9) |
| N3 | 0.0231 (12) | 0.0284 (13) | 0.0282 (13) | 0.0007 (10) | 0.0083 (10) | 0.0018 (10) |
| O2 | 0.0157 (8) | 0.0225 (9) | 0.0151 (9) | −0.0011 (7) | 0.0056 (7) | 0.0000 (7) |
| C10 | 0.0179 (12) | 0.0165 (11) | 0.0167 (12) | −0.0006 (9) | 0.0038 (9) | −0.0032 (9) |
| C11 | 0.0189 (12) | 0.0195 (12) | 0.0239 (13) | 0.0014 (10) | 0.0091 (10) | 0.0020 (10) |
| C12 | 0.0171 (12) | 0.0222 (13) | 0.0295 (15) | 0.0033 (10) | 0.0049 (11) | 0.0042 (11) |
| C13 | 0.0261 (14) | 0.0271 (14) | 0.0253 (14) | 0.0058 (11) | 0.0057 (11) | 0.0074 (11) |
| C14 | 0.0241 (13) | 0.0227 (13) | 0.0219 (13) | 0.0020 (10) | 0.0071 (11) | 0.0031 (10) |
| C15 | 0.0194 (12) | 0.0178 (12) | 0.0192 (12) | 0.0003 (9) | 0.0077 (10) | 0.0005 (9) |
| C16 | 0.0234 (13) | 0.0211 (12) | 0.0203 (13) | −0.0021 (10) | 0.0121 (11) | 0.0000 (10) |
| N4 | 0.0155 (10) | 0.0221 (11) | 0.0188 (11) | −0.0031 (8) | 0.0092 (8) | −0.0009 (8) |
| C17 | 0.0155 (12) | 0.0356 (15) | 0.0204 (13) | −0.0018 (11) | 0.0084 (10) | 0.0014 (11) |
| C18 | 0.0185 (12) | 0.0295 (14) | 0.0205 (13) | 0.0013 (10) | 0.0082 (10) | −0.0025 (11) |
| Ni1 | 0.0168 (2) | 0.0196 (2) | 0.0167 (2) | −0.00043 (17) | 0.00499 (18) | −0.00011 (17) |
| C19 | 0.0179 (13) | 0.0315 (15) | 0.0223 (14) | 0.0001 (10) | 0.0077 (11) | −0.0021 (11) |
| N5 | 0.0202 (11) | 0.0236 (11) | 0.0187 (11) | −0.0001 (9) | 0.0053 (9) | −0.0027 (9) |
| C20 | 0.0256 (13) | 0.0237 (13) | 0.0241 (13) | −0.0018 (11) | 0.0089 (11) | 0.0020 (11) |
| C21 | 0.0316 (15) | 0.0248 (14) | 0.0198 (13) | 0.0036 (11) | 0.0087 (11) | 0.0025 (10) |
| N6 | 0.0221 (11) | 0.0230 (11) | 0.0176 (11) | 0.0009 (9) | 0.0038 (9) | −0.0010 (9) |
| C22 | 0.0224 (13) | 0.0257 (14) | 0.0227 (13) | 0.0042 (11) | 0.0041 (11) | −0.0007 (11) |
| C23 | 0.0218 (13) | 0.0303 (15) | 0.0235 (14) | 0.0040 (11) | 0.0060 (11) | −0.0025 (11) |
| C24 | 0.0296 (15) | 0.0342 (17) | 0.0319 (16) | −0.0043 (13) | 0.0059 (13) | 0.0031 (13) |
| O3 | 0.0240 (10) | 0.0339 (11) | 0.0288 (11) | −0.0053 (9) | 0.0058 (9) | 0.0000 (9) |
| O1—C1 | 1.313 (3) | C16—H10 | 0.9300 |
| O1—Cr1 | 1.930 (2) | N4—C17 | 1.472 (3) |
| C1—C2 | 1.413 (4) | C17—C18 | 1.525 (4) |
| C1—C6 | 1.420 (4) | C17—H11 | 0.9700 |
| C2—C3 | 1.384 (4) | C17—H12 | 0.9700 |
| C2—H1 | 0.9300 | C18—H13 | 0.9700 |
| C3—C4 | 1.383 (5) | C18—H14 | 0.9700 |
| C3—H2 | 0.9300 | Ni1—N6i | 2.086 (2) |
| C4—C5 | 1.376 (5) | Ni1—N6 | 2.086 (2) |
| C4—H3 | 0.9300 | Ni1—N5i | 2.092 (2) |
| C5—C6 | 1.413 (4) | Ni1—N5 | 2.092 (2) |
| C5—H4 | 0.9300 | Ni1—N3i | 2.117 (3) |
| C6—C7 | 1.443 (4) | C19—N5 | 1.473 (4) |
| C7—N1 | 1.285 (4) | C19—C23i | 1.531 (4) |
| C7—H5 | 0.9300 | C19—H15 | 0.9700 |
| N1—C18 | 1.467 (3) | C19—H16 | 0.9700 |
| N1—Cr1 | 2.011 (2) | N5—C20 | 1.480 (4) |
| Cr1—O2 | 1.9464 (19) | N5—H17 | 0.9100 |
| Cr1—N4 | 2.010 (2) | C20—C21 | 1.521 (4) |
| Cr1—C8 | 2.080 (3) | C20—H18 | 0.9700 |
| Cr1—C9 | 2.103 (2) | C20—H19 | 0.9700 |
| C8—N2 | 1.148 (4) | C21—N6 | 1.485 (4) |
| C9—N3 | 1.156 (4) | C21—H20 | 0.9700 |
| N3—Ni1 | 2.117 (3) | C21—H21 | 0.9700 |
| O2—C10 | 1.322 (3) | N6—C22 | 1.478 (4) |
| C10—C11 | 1.408 (4) | N6—H22 | 0.9100 |
| C10—C15 | 1.429 (4) | C22—C23 | 1.513 (4) |
| C11—C12 | 1.379 (4) | C22—H23 | 0.9700 |
| C11—H6 | 0.9300 | C22—H24 | 0.9700 |
| C12—C13 | 1.396 (4) | C23—C19i | 1.531 (4) |
| C12—H7 | 0.9300 | C23—H25 | 0.9700 |
| C13—C14 | 1.378 (4) | C23—H26 | 0.9700 |
| C13—H8 | 0.9300 | C24—O3 | 1.420 (4) |
| C14—C15 | 1.406 (4) | C24—H27 | 0.9600 |
| C14—H9 | 0.9300 | C24—H28 | 0.9600 |
| C15—C16 | 1.453 (4) | C24—H29 | 0.9600 |
| C16—N4 | 1.277 (4) | O3—H30 | 0.8200 |
| C1—O1—Cr1 | 126.52 (18) | C18—C17—H12 | 110.3 |
| O1—C1—C2 | 118.7 (3) | H11—C17—H12 | 108.6 |
| O1—C1—C6 | 124.3 (2) | N1—C18—C17 | 107.9 (2) |
| C2—C1—C6 | 117.0 (3) | N1—C18—H13 | 110.1 |
| C3—C2—C1 | 121.3 (3) | C17—C18—H13 | 110.1 |
| C3—C2—H1 | 119.4 | N1—C18—H14 | 110.1 |
| C1—C2—H1 | 119.4 | C17—C18—H14 | 110.1 |
| C4—C3—C2 | 121.4 (3) | H13—C18—H14 | 108.4 |
| C4—C3—H2 | 119.3 | N6i—Ni1—N6 | 180.000 (1) |
| C2—C3—H2 | 119.3 | N6i—Ni1—N5i | 85.37 (9) |
| C5—C4—C3 | 118.9 (3) | N6—Ni1—N5i | 94.63 (9) |
| C5—C4—H3 | 120.6 | N6i—Ni1—N5 | 94.63 (9) |
| C3—C4—H3 | 120.6 | N6—Ni1—N5 | 85.37 (9) |
| C4—C5—C6 | 121.2 (3) | N5i—Ni1—N5 | 180.0 |
| C4—C5—H4 | 119.4 | N6i—Ni1—N3i | 90.15 (10) |
| C6—C5—H4 | 119.4 | N6—Ni1—N3i | 89.85 (10) |
| C5—C6—C1 | 120.1 (3) | N5i—Ni1—N3i | 92.54 (10) |
| C5—C6—C7 | 116.4 (3) | N5—Ni1—N3i | 87.46 (9) |
| C1—C6—C7 | 123.4 (2) | N6i—Ni1—N3 | 89.85 (10) |
| N1—C7—C6 | 124.4 (3) | N6—Ni1—N3 | 90.15 (10) |
| N1—C7—H5 | 117.8 | N5i—Ni1—N3 | 87.46 (9) |
| C6—C7—H5 | 117.8 | N5—Ni1—N3 | 92.54 (10) |
| C7—N1—C18 | 121.3 (2) | N3i—Ni1—N3 | 180.0 |
| C7—N1—Cr1 | 126.18 (19) | N5—C19—C23i | 111.5 (2) |
| C18—N1—Cr1 | 112.47 (17) | N5—C19—H15 | 109.3 |
| O1—Cr1—O2 | 94.74 (8) | C23i—C19—H15 | 109.3 |
| O1—Cr1—N4 | 172.76 (9) | N5—C19—H16 | 109.3 |
| O2—Cr1—N4 | 92.47 (9) | C23i—C19—H16 | 109.3 |
| O1—Cr1—N1 | 90.82 (9) | H15—C19—H16 | 108.0 |
| O2—Cr1—N1 | 173.49 (9) | C19—N5—C20 | 113.8 (2) |
| N4—Cr1—N1 | 82.02 (10) | C19—N5—Ni1 | 115.47 (18) |
| O1—Cr1—C8 | 92.10 (10) | C20—N5—Ni1 | 105.70 (17) |
| O2—Cr1—C8 | 93.88 (10) | C19—N5—H17 | 107.2 |
| N4—Cr1—C8 | 86.81 (10) | C20—N5—H17 | 107.2 |
| N1—Cr1—C8 | 89.29 (10) | Ni1—N5—H17 | 107.2 |
| O1—Cr1—C9 | 95.82 (9) | N5—C20—C21 | 109.1 (2) |
| O2—Cr1—C9 | 86.51 (9) | N5—C20—H18 | 109.9 |
| N4—Cr1—C9 | 85.20 (10) | C21—C20—H18 | 109.9 |
| N1—Cr1—C9 | 89.57 (9) | N5—C20—H19 | 109.9 |
| C8—Cr1—C9 | 172.01 (11) | C21—C20—H19 | 109.9 |
| N2—C8—Cr1 | 177.7 (3) | H18—C20—H19 | 108.3 |
| N3—C9—Cr1 | 164.0 (2) | N6—C21—C20 | 109.1 (2) |
| C9—N3—Ni1 | 170.0 (2) | N6—C21—H20 | 109.9 |
| C10—O2—Cr1 | 125.54 (16) | C20—C21—H20 | 109.9 |
| O2—C10—C11 | 118.3 (2) | N6—C21—H21 | 109.9 |
| O2—C10—C15 | 124.7 (2) | C20—C21—H21 | 109.9 |
| C11—C10—C15 | 117.0 (2) | H20—C21—H21 | 108.3 |
| C12—C11—C10 | 122.0 (3) | C22—N6—C21 | 113.6 (2) |
| C12—C11—H6 | 119.0 | C22—N6—Ni1 | 114.53 (18) |
| C10—C11—H6 | 119.0 | C21—N6—Ni1 | 105.33 (17) |
| C11—C12—C13 | 120.8 (3) | C22—N6—H22 | 107.7 |
| C11—C12—H7 | 119.6 | C21—N6—H22 | 107.7 |
| C13—C12—H7 | 119.6 | Ni1—N6—H22 | 107.7 |
| C14—C13—C12 | 118.7 (3) | N6—C22—C23 | 112.8 (2) |
| C14—C13—H8 | 120.6 | N6—C22—H23 | 109.0 |
| C12—C13—H8 | 120.6 | C23—C22—H23 | 109.0 |
| C13—C14—C15 | 121.7 (3) | N6—C22—H24 | 109.0 |
| C13—C14—H9 | 119.1 | C23—C22—H24 | 109.0 |
| C15—C14—H9 | 119.1 | H23—C22—H24 | 107.8 |
| C14—C15—C10 | 119.7 (2) | C22—C23—C19i | 116.1 (2) |
| C14—C15—C16 | 116.1 (2) | C22—C23—H25 | 108.3 |
| C10—C15—C16 | 124.2 (2) | C19i—C23—H25 | 108.3 |
| N4—C16—C15 | 124.6 (2) | C22—C23—H26 | 108.3 |
| N4—C16—H10 | 117.7 | C19i—C23—H26 | 108.3 |
| C15—C16—H10 | 117.7 | H25—C23—H26 | 107.4 |
| C16—N4—C17 | 121.2 (2) | O3—C24—H27 | 109.5 |
| C16—N4—Cr1 | 125.90 (19) | O3—C24—H28 | 109.5 |
| C17—N4—Cr1 | 112.89 (17) | H27—C24—H28 | 109.5 |
| N4—C17—C18 | 107.0 (2) | O3—C24—H29 | 109.5 |
| N4—C17—H11 | 110.3 | H27—C24—H29 | 109.5 |
| C18—C17—H11 | 110.3 | H28—C24—H29 | 109.5 |
| N4—C17—H12 | 110.3 | C24—O3—H30 | 109.5 |
| Symmetry codes: (i) −x+2, −y, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H30···O2ii | 0.82 | 2.18 | 2.989 (3) | 168 |
| N5—H17···O3iii | 0.91 | 2.34 | 3.212 (3) | 161 |
| C17—H12···N2iv | 0.97 | 2.56 | 3.467 (4) | 156 |
| Symmetry codes: (ii) x, y, z−1; (iii) −x+2, −y, −z+1; (iv) x, −y+1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H30···O2i | 0.82 | 2.18 | 2.989 (3) | 168 |
| N5—H17···O3ii | 0.91 | 2.34 | 3.212 (3) | 161 |
| C17—H12···N2iii | 0.97 | 2.56 | 3.467 (4) | 156 |
| Symmetry codes: (i) x, y, z−1; (ii) −x+2, −y, −z+1; (iii) x, −y+1/2, z−1/2. |
This work was supported by NY208044, 09KJB150008 and in part by the National Basic Research Program of China (2009CB930601).
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Cyanide-bridged infinite systems (or Prussian blue analogues) and high-spin clusters have attracted great research interest due to their unique magnetic properties, including high-Tc superconducting magnets and photoinduced magnetization. Among these interesting researches, low-dimensional complexes as well as polynuclear clusters have attracted special attention, because they can be used to investigate the inter-metallic magnetic coupling quantitatively (Lescouëzec et al., 2005).
Recently, a new cyanide-containing building block K[Cr(salen)(CN)2] (salen2- = N,N'- bis(salicyl)ethylenediaminate) with two trans cyanide groups has been exploited to assemble cyanide-bridged low-dimensional complexes (Ni et al., 2008). By using this new building block, we report here the synthesis and crystal structure of the title compound, [Cr(salen)(CN)2]2[Ni(cyclam)].CH3OH.
Complex I consists of a trinuclear cluster and one methanol solvate molecule. As shown in Fig. 1, in this trinuclear cluster, the [Cr(salen)(CN)2] unit acts as a monodentate ligand through one of its two cyanide groups toward a central [Ni(cyclam)]2+ core. The nickel atom is in an axially elongated octahedral environment. Four nitrogen atoms from the cyclam ligand form the equatorial plane. Two cyanide nitrogen atoms occupy the axial positions. The complex are linked with the methanol solvate molecules via O—H···O and N—H···O hydrogen bonds (Fig. 2). The individual complex molecules are linked by C—H···N hydrogen bonds to form chains along b.