Acta Cryst. (2011). E67, m845 [ doi:10.1107/S1600536811020022 ]
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O)terbium(III) octacyanidomolybdate(V)In the title compound, [Tb(C10H8N2O2)4(H2O)4][Mo(CN)8], both metal atoms are eight-coordinated. The TbIII atom displays a dodecahedral geometry, while the MoV ion exhibits a distorted square-antiprismatic geometry. The Tb atoms are located on a special position of site symmetry 
, whereas the Mo atoms are located on a twofold rotation axis. The cations are linked by O-H
O hydrogen bonds.
Single crystals of the title compound were prepared at room temperature in the dark by slow diffusion of a H2O solution (3 ml) containing Tb(NO3)3.6H2O (0.05 mmol) and 4,4'-dpdo (0.05 mmol) into a CH3CN solution (15 ml) of [HN(n-C4H9)3]3[Mo(CN)8].4H2O (0.05 mmol) (Bok et al., 1975). After two weeks, yellow block crystals were obtained.
The H atoms of 4,4'-bipyridine dioxide ligands were ideally positioned with C—H = 0.93 Å and included in the refinement using a riding model with U(H) set to 1.2 Ueq(C). The H atoms bound to oxygen atoms were located from difference maps and refined as riding with U(H) set to 1.2 Ueq(O).
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bt5505fig1thm.gif)
| Fig. 1. ORTEP diagram of the title compound. Hydrogen atoms have been omitted for clarity and thermal ellipsoids are presented at the 30% probability level. |
![[Figure 2]](./bt5505fig2thm.gif)
| Fig. 2. Perspective view of the title compound in ab plane. Hydrogen atoms and coordinated water molecules have been omitted for clarity. |
| [Tb(C10H8N2O2)4(H2O)4][Mo(CN)8] | Dx = 1.688 Mg m−3 |
| Mr = 1287.72 | Mo Kα radiation, λ = 0.71073 Å |
| Tetragonal, P4/n | Cell parameters from 9881 reflections |
| Hall symbol: -P 4a | θ = 2.3–27.5° |
| a = 17.9226 (7) Å | µ = 1.71 mm−1 |
| c = 7.8877 (6) Å | T = 291 K |
| V = 2533.7 (2) Å3 | Block, yellow |
| Z = 2 | 0.22 × 0.21 × 0.12 mm |
| F(000) = 1286 |
| Bruker SMART APEX CCD diffractometer | 2730 reflections with I > 2σ(I) |
| graphite | Rint = 0.026 |
| φ and ω scans | θmax = 27.5°, θmin = 1.6° |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −23→23 |
| Tmin = 0.693, Tmax = 0.843 | k = −23→23 |
| 21243 measured reflections | l = −10→10 |
| 2921 independent 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)] = 0.016 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.043 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0183P)2 + 1.8165P] where P = (Fo2 + 2Fc2)/3 |
| 2921 reflections | (Δ/σ)max = 0.001 |
| 177 parameters | Δρmax = 0.36 e Å−3 |
| 0 restraints | Δρmin = −0.29 e Å−3 |
| [Tb(C10H8N2O2)4(H2O)4][Mo(CN)8] | Z = 2 |
| Mr = 1287.72 | Mo Kα radiation |
| Tetragonal, P4/n | µ = 1.71 mm−1 |
| a = 17.9226 (7) Å | T = 291 K |
| c = 7.8877 (6) Å | 0.22 × 0.21 × 0.12 mm |
| V = 2533.7 (2) Å3 |
| Bruker SMART APEX CCD diffractometer | 2921 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2730 reflections with I > 2σ(I) |
| Tmin = 0.693, Tmax = 0.843 | Rint = 0.026 |
| 21243 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.016 | H-atom parameters constrained |
| wR(F2) = 0.043 | Δρmax = 0.36 e Å−3 |
| S = 1.08 | Δρmin = −0.29 e Å−3 |
| 2921 reflections | Absolute structure: ? |
| 177 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| Tb1 | 0.7500 | 0.2500 | 0.0000 | 0.01136 (5) | |
| Mo1 | 0.7500 | 0.7500 | −0.24987 (4) | 0.02019 (7) | |
| O1 | 0.64962 (6) | 0.17736 (7) | 0.10113 (14) | 0.0251 (3) | |
| O2 | 0.27973 (7) | −0.11246 (7) | −0.50459 (14) | 0.0223 (2) | |
| O3 | 0.70614 (6) | 0.31664 (6) | 0.24591 (13) | 0.0183 (2) | |
| N1 | 0.60473 (10) | 0.81932 (10) | −0.4592 (3) | 0.0422 (4) | |
| N2 | 0.59644 (10) | 0.70470 (10) | −0.0373 (3) | 0.0393 (4) | |
| N3 | 0.60104 (8) | 0.13848 (8) | 0.00837 (16) | 0.0201 (3) | |
| N4 | 0.33441 (7) | −0.07064 (7) | −0.44088 (17) | 0.0176 (2) | |
| C1 | 0.65693 (10) | 0.79577 (9) | −0.3922 (3) | 0.0300 (4) | |
| C2 | 0.65123 (10) | 0.71973 (9) | −0.1057 (3) | 0.0293 (4) | |
| C3 | 0.62224 (9) | 0.07458 (9) | −0.0674 (2) | 0.0234 (3) | |
| H3 | 0.6709 | 0.0575 | −0.0537 | 0.028* | |
| C4 | 0.57297 (9) | 0.03404 (9) | −0.1648 (2) | 0.0215 (3) | |
| H4 | 0.5888 | −0.0098 | −0.2166 | 0.026* | |
| C5 | 0.49930 (8) | 0.05822 (8) | −0.1867 (2) | 0.0175 (3) | |
| C6 | 0.47918 (9) | 0.12409 (9) | −0.1031 (2) | 0.0248 (3) | |
| H6 | 0.4306 | 0.1419 | −0.1129 | 0.030* | |
| C7 | 0.53013 (10) | 0.16301 (10) | −0.0063 (2) | 0.0257 (4) | |
| H7 | 0.5155 | 0.2064 | 0.0491 | 0.031* | |
| C8 | 0.44383 (8) | 0.01450 (8) | −0.28394 (19) | 0.0168 (3) | |
| C9 | 0.45913 (8) | −0.05724 (8) | −0.3460 (2) | 0.0182 (3) | |
| H9 | 0.5070 | −0.0768 | −0.3356 | 0.022* | |
| C10 | 0.40389 (8) | −0.09908 (8) | −0.4224 (2) | 0.0189 (3) | |
| H10 | 0.4144 | −0.1469 | −0.4613 | 0.023* | |
| C12 | 0.37208 (9) | 0.04249 (8) | −0.3126 (2) | 0.0209 (3) | |
| H12 | 0.3604 | 0.0907 | −0.2780 | 0.025* | |
| C13 | 0.31847 (9) | −0.00028 (9) | −0.3913 (2) | 0.0217 (3) | |
| H13 | 0.2712 | 0.0193 | −0.4103 | 0.026* | |
| H3WA | 0.6727 | 0.3040 | 0.3134 | 0.033* | |
| H3WB | 0.7363 | 0.3368 | 0.3136 | 0.033* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Tb1 | 0.01183 (5) | 0.01183 (5) | 0.01043 (7) | 0.000 | 0.000 | 0.000 |
| Mo1 | 0.01407 (8) | 0.01407 (8) | 0.03243 (15) | 0.000 | 0.000 | 0.000 |
| O1 | 0.0234 (6) | 0.0348 (6) | 0.0171 (5) | −0.0157 (5) | −0.0019 (5) | −0.0008 (5) |
| O2 | 0.0190 (5) | 0.0247 (6) | 0.0231 (6) | −0.0067 (4) | −0.0023 (4) | −0.0059 (4) |
| O3 | 0.0179 (5) | 0.0232 (5) | 0.0139 (5) | −0.0007 (4) | 0.0019 (4) | −0.0032 (4) |
| N1 | 0.0310 (9) | 0.0290 (8) | 0.0666 (12) | −0.0020 (7) | −0.0123 (9) | 0.0126 (8) |
| N2 | 0.0297 (8) | 0.0313 (8) | 0.0569 (11) | 0.0000 (7) | 0.0099 (8) | 0.0101 (8) |
| N3 | 0.0188 (6) | 0.0246 (7) | 0.0170 (6) | −0.0095 (5) | −0.0005 (5) | 0.0018 (5) |
| N4 | 0.0183 (6) | 0.0198 (6) | 0.0146 (6) | −0.0043 (5) | −0.0004 (5) | −0.0006 (5) |
| C1 | 0.0243 (8) | 0.0195 (8) | 0.0462 (11) | −0.0031 (6) | −0.0026 (8) | 0.0050 (7) |
| C2 | 0.0241 (8) | 0.0201 (8) | 0.0438 (11) | 0.0008 (6) | 0.0020 (8) | 0.0045 (7) |
| C3 | 0.0166 (7) | 0.0280 (8) | 0.0257 (8) | −0.0021 (6) | −0.0004 (6) | 0.0010 (7) |
| C4 | 0.0189 (7) | 0.0217 (7) | 0.0239 (8) | −0.0016 (6) | 0.0000 (6) | −0.0011 (6) |
| C5 | 0.0177 (7) | 0.0172 (7) | 0.0176 (7) | −0.0041 (5) | 0.0004 (6) | 0.0026 (6) |
| C6 | 0.0186 (7) | 0.0210 (8) | 0.0349 (9) | −0.0013 (6) | −0.0035 (7) | −0.0042 (7) |
| C7 | 0.0230 (8) | 0.0215 (8) | 0.0328 (9) | −0.0044 (6) | 0.0002 (7) | −0.0052 (7) |
| C8 | 0.0173 (7) | 0.0163 (7) | 0.0168 (7) | −0.0037 (5) | 0.0011 (5) | 0.0019 (5) |
| C9 | 0.0162 (7) | 0.0188 (7) | 0.0198 (7) | −0.0004 (5) | 0.0022 (6) | 0.0009 (6) |
| C10 | 0.0203 (7) | 0.0171 (7) | 0.0191 (7) | −0.0006 (5) | 0.0030 (6) | −0.0018 (6) |
| C12 | 0.0222 (7) | 0.0166 (7) | 0.0241 (8) | 0.0009 (6) | −0.0023 (6) | −0.0016 (6) |
| C13 | 0.0192 (7) | 0.0213 (7) | 0.0246 (8) | 0.0022 (6) | −0.0034 (6) | −0.0026 (6) |
| Tb1—O1i | 2.3596 (11) | N3—C3 | 1.346 (2) |
| Tb1—O1ii | 2.3596 (11) | N3—C7 | 1.350 (2) |
| Tb1—O1 | 2.3596 (11) | N4—C13 | 1.351 (2) |
| Tb1—O1iii | 2.3596 (11) | N4—C10 | 1.3533 (19) |
| Tb1—O3i | 2.4097 (10) | C3—C4 | 1.378 (2) |
| Tb1—O3ii | 2.4097 (10) | C3—H3 | 0.9300 |
| Tb1—O3 | 2.4097 (10) | C4—C5 | 1.400 (2) |
| Tb1—O3iii | 2.4097 (10) | C4—H4 | 0.9300 |
| Mo1—C1iv | 2.1715 (18) | C5—C6 | 1.400 (2) |
| Mo1—C1 | 2.1715 (18) | C5—C8 | 1.480 (2) |
| Mo1—C1v | 2.1715 (18) | C6—C7 | 1.379 (2) |
| Mo1—C1vi | 2.1715 (18) | C6—H6 | 0.9300 |
| Mo1—C2iv | 2.1731 (18) | C7—H7 | 0.9300 |
| Mo1—C2 | 2.1731 (18) | C8—C12 | 1.399 (2) |
| Mo1—C2vi | 2.1731 (18) | C8—C9 | 1.403 (2) |
| Mo1—C2v | 2.1731 (18) | C9—C10 | 1.380 (2) |
| O1—N3 | 1.3338 (17) | C9—H9 | 0.9300 |
| O2—N4 | 1.3323 (16) | C10—H10 | 0.9300 |
| O3—H3WA | 0.8326 | C12—C13 | 1.377 (2) |
| O3—H3WB | 0.8422 | C12—H12 | 0.9300 |
| N1—C1 | 1.155 (2) | C13—H13 | 0.9300 |
| N2—C2 | 1.152 (2) | ||
| O1i—Tb1—O1ii | 96.562 (17) | C1iv—Mo1—C2v | 143.33 (6) |
| O1i—Tb1—O1 | 96.562 (17) | C1—Mo1—C2v | 76.77 (7) |
| O1ii—Tb1—O1 | 140.48 (5) | C1v—Mo1—C2v | 74.88 (7) |
| O1i—Tb1—O1iii | 140.48 (5) | C1vi—Mo1—C2v | 140.36 (6) |
| O1ii—Tb1—O1iii | 96.562 (17) | C2iv—Mo1—C2v | 116.87 (11) |
| O1—Tb1—O1iii | 96.562 (17) | C2—Mo1—C2v | 74.10 (5) |
| O1i—Tb1—O3i | 75.68 (4) | C2vi—Mo1—C2v | 74.10 (5) |
| O1ii—Tb1—O3i | 146.10 (4) | N3—O1—Tb1 | 126.90 (9) |
| O1—Tb1—O3i | 73.39 (4) | Tb1—O3—H3WA | 128.0 |
| O1iii—Tb1—O3i | 72.73 (4) | Tb1—O3—H3WB | 120.9 |
| O1i—Tb1—O3ii | 73.39 (4) | H3WA—O3—H3WB | 100.0 |
| O1ii—Tb1—O3ii | 75.68 (4) | O1—N3—C3 | 120.24 (14) |
| O1—Tb1—O3ii | 72.73 (4) | O1—N3—C7 | 119.45 (14) |
| O1iii—Tb1—O3ii | 146.10 (4) | C3—N3—C7 | 120.30 (14) |
| O3i—Tb1—O3ii | 130.38 (3) | O2—N4—C13 | 118.60 (13) |
| O1i—Tb1—O3 | 146.10 (4) | O2—N4—C10 | 120.38 (13) |
| O1ii—Tb1—O3 | 72.73 (4) | C13—N4—C10 | 121.00 (13) |
| O1—Tb1—O3 | 75.68 (4) | N1—C1—Mo1 | 175.79 (19) |
| O1iii—Tb1—O3 | 73.39 (4) | N2—C2—Mo1 | 176.07 (18) |
| O3i—Tb1—O3 | 130.38 (3) | N3—C3—C4 | 121.02 (15) |
| O3ii—Tb1—O3 | 72.79 (5) | N3—C3—H3 | 119.5 |
| O1i—Tb1—O3iii | 72.73 (4) | C4—C3—H3 | 119.5 |
| O1ii—Tb1—O3iii | 73.39 (4) | C3—C4—C5 | 120.65 (15) |
| O1—Tb1—O3iii | 146.10 (4) | C3—C4—H4 | 119.7 |
| O1iii—Tb1—O3iii | 75.68 (4) | C5—C4—H4 | 119.7 |
| O3i—Tb1—O3iii | 72.79 (5) | C6—C5—C4 | 116.49 (14) |
| O3ii—Tb1—O3iii | 130.38 (3) | C6—C5—C8 | 121.17 (14) |
| O3—Tb1—O3iii | 130.38 (3) | C4—C5—C8 | 122.23 (14) |
| C1iv—Mo1—C1 | 74.50 (5) | C7—C6—C5 | 121.10 (15) |
| C1iv—Mo1—C1v | 117.74 (11) | C7—C6—H6 | 119.4 |
| C1—Mo1—C1v | 74.50 (5) | C5—C6—H6 | 119.4 |
| C1iv—Mo1—C1vi | 74.50 (5) | N3—C7—C6 | 120.42 (16) |
| C1—Mo1—C1vi | 117.74 (11) | N3—C7—H7 | 119.8 |
| C1v—Mo1—C1vi | 74.50 (5) | C6—C7—H7 | 119.8 |
| C1iv—Mo1—C2iv | 74.88 (7) | C12—C8—C9 | 116.87 (14) |
| C1—Mo1—C2iv | 140.36 (6) | C12—C8—C5 | 120.77 (13) |
| C1v—Mo1—C2iv | 143.33 (6) | C9—C8—C5 | 122.32 (13) |
| C1vi—Mo1—C2iv | 76.77 (7) | C10—C9—C8 | 120.66 (14) |
| C1iv—Mo1—C2 | 76.77 (7) | C10—C9—H9 | 119.7 |
| C1—Mo1—C2 | 74.88 (7) | C8—C9—H9 | 119.7 |
| C1v—Mo1—C2 | 140.36 (6) | N4—C10—C9 | 120.16 (14) |
| C1vi—Mo1—C2 | 143.33 (6) | N4—C10—H10 | 119.9 |
| C2iv—Mo1—C2 | 74.10 (5) | C9—C10—H10 | 119.9 |
| C1iv—Mo1—C2vi | 140.36 (6) | C13—C12—C8 | 120.98 (14) |
| C1—Mo1—C2vi | 143.33 (6) | C13—C12—H12 | 119.5 |
| C1v—Mo1—C2vi | 76.77 (7) | C8—C12—H12 | 119.5 |
| C1vi—Mo1—C2vi | 74.88 (7) | N4—C13—C12 | 120.17 (14) |
| C2iv—Mo1—C2vi | 74.10 (5) | N4—C13—H13 | 119.9 |
| C2—Mo1—C2vi | 116.87 (11) | C12—C13—H13 | 119.9 |
| Symmetry codes: (i) −y+1, x−1/2, −z; (ii) −x+3/2, −y+1/2, z; (iii) y+1/2, −x+1, −z; (iv) −y+3/2, x, z; (v) y, −x+3/2, z; (vi) −x+3/2, −y+3/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3WA···O2vii | 0.83 | 1.85 | 2.6702 (15) | 169 |
| O3—H3WB···O2viii | 0.84 | 1.92 | 2.7417 (16) | 164 |
| O3—H3WB···N4viii | 0.84 | 2.62 | 3.4251 (16) | 161 |
| Symmetry codes: (vii) −y+1/2, x, z+1; (viii) x+1/2, y+1/2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3WA···O2i | 0.83 | 1.85 | 2.6702 (15) | 169 |
| O3—H3WB···O2ii | 0.84 | 1.92 | 2.7417 (16) | 164 |
| O3—H3WB···N4ii | 0.84 | 2.62 | 3.4251 (16) | 161 |
| Symmetry codes: (i) −y+1/2, x, z+1; (ii) x+1/2, y+1/2, −z. |
The work was supported by the Project of the Priority Academic Program Development of Jiangsu Higher Education Institutions.
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In the past few years, octacyanometallate-based complexes have attracted considerable attention in the field of cyanide-bridged hetero-metallic system. Many assemblies based on [MV(CN)8]3- (M = Mo or W) and lanthanide ions can take a variety of structures (Chelebaeva et al., 2009; Kozieł et al., 2010; Ma et al., 2009; Przychodzeń et al., 2007; Qian et al., 2010; Wang et al., 2006; Zhou et al., 2010). Recently, we have used [Mo(CN)8]3- as a building block to react with Tb3+ and 4,4'-bipyridine dioxide (4,4'-dpdo) obtaining a new ionic complex, [Tb(4,4'-bpdo)4(H2O)4][Mo(CN)8.
In the structure, the eight-coordinated TbIII center displays a decahedron geometry, while each [MoV(CN)8] moiety exhibits a distorted square antiprismic geometry. The average values of Mo—C and C—N bond distances are 2.171 and 1.155 Å, respectively, while the Mo—C—N units are nearly linear. The anions are linked by O-H..O hydrogen bonds.