Acta Cryst. (2009). E65, i79-i80 [ doi:10.1107/S1600536809039336 ]
The asymmetric unit of the title compound, KI4[MoIII(CN)7]·2H2O, consists of one [Mo(CN)7]4- anion, four K+ cations, and two water molecules. The [MoIII(CN)7]4- anion has a seven-coordinated capped-trigonal-prismatic coordination geometry. The site-occupancy factors of the disordered water molecules were set at 0.90, 0.60 and 0.50. The H-atom positions could not be determined for two of the water molecules. The H atoms of the water with a site-occupancy factor of 0.90 were refined using O-H and H
H distance restraints.
The title compound was prepared by reacting (NH4)2[MoCl5(H2O)] (1.81 g) with KCN (4 g) in H2O (23 ml) at room temperature. The prepared compound was a green plate-type crystal. Elemental analyses: calcd for KI4[MoIII(CN)7]2.75H2O, Calculated: Mo, 19.82%; C, 17.37%; H, 1.15%; N, 20.26%. Found: Mo, 19.44%; C, 17.65%; H, 1.13%; N, 20.01%. In the Infrared (IR) spectra, cyano stretching peaks were observed at 2114 and 2069 cm-1.
The H atoms of the solvent water molecules, O2 and O3, could not be located. The maximum and minimum residual electron density peaks were located 0.18 and 0.91 Å from the K3 atom and the Mo1 atom, respectively.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2007); software used to prepare material for publication: ORTEP-3 (Farrugia, 1997) and PyMOLWin (DeLano, 2007).
![[Figure 1]](./si2189fig1thm.gif)
| Fig. 1. Thermal ellipsoid plots (50% probability level) of independent atoms of KI4[MoIII(CN)7]2H2O. Positions of hydrogen atoms of the disordered water molecules could not be determined. |
| K4[Mo(CN)7]·2H2O | Z = 2 |
| Mr = 468.29 | F(000) = 454 |
| Triclinic, P1 | Dx = 2.067 Mg m−3 |
| a = 8.8813 (5) Å | Mo Kα radiation, λ = 0.71075 Å |
| b = 9.2896 (4) Å | Cell parameters from 6568 reflections |
| c = 9.7221 (4) Å | θ = 3.0–27.5° |
| α = 86.6480 (13)° | µ = 1.99 mm−1 |
| β = 82.2150 (19)° | T = 90 K |
| γ = 71.2570 (17)° | Platelet, green |
| V = 752.48 (6) Å3 | 0.10 × 0.05 × 0.02 mm |
| Rigaku R-AXIS RAPID diffractometer | 3421 independent reflections |
| Radiation source: fine-focus sealed tube | 2893 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| ω scans | θmax = 27.5°, θmin = 3.0° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1999) | h = −11→11 |
| Tmin = 0.826, Tmax = 0.961 | k = −12→11 |
| 7367 measured reflections | l = −12→11 |
| 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 | H-atom parameters not defined |
| wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.0908P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.25 | (Δ/σ)max < 0.001 |
| 3421 reflections | Δρmax = 2.85 e Å−3 |
| 210 parameters | Δρmin = −1.08 e Å−3 |
| 3 restraints |
| K4[Mo(CN)7]·2H2O | γ = 71.2570 (17)° |
| Mr = 468.29 | V = 752.48 (6) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.8813 (5) Å | Mo Kα radiation |
| b = 9.2896 (4) Å | µ = 1.99 mm−1 |
| c = 9.7221 (4) Å | T = 90 K |
| α = 86.6480 (13)° | 0.10 × 0.05 × 0.02 mm |
| β = 82.2150 (19)° |
| Rigaku R-AXIS RAPID diffractometer | 3421 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1999) | 2893 reflections with I > 2σ(I) |
| Tmin = 0.826, Tmax = 0.961 | Rint = 0.025 |
| 7367 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.054 | H-atom parameters not defined |
| wR(F2) = 0.153 | Δρmax = 2.85 e Å−3 |
| S = 1.25 | Δρmin = −1.08 e Å−3 |
| 3421 reflections | Absolute structure: ? |
| 210 parameters | Flack parameter: ? |
| 3 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. Some weak peaks appeared around all O atoms (O1, O2, and O3). Although we could assign the H atoms of O1 with restraints of DFIX (O—H 0.85 0.02 Å and H···H distances about 1.38 0.02 Å), the H atoms of O2 and O3 could not be placed using restraints of DFIX. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Mo1 | −0.28013 (4) | 0.18814 (3) | 0.22632 (3) | 0.00989 (16) | |
| K4 | 0.28925 (10) | 0.01355 (9) | 0.17415 (9) | 0.0124 (2) | |
| K1 | 0.27995 (11) | −0.37242 (10) | 0.36699 (9) | 0.0146 (2) | |
| K2 | −0.28226 (10) | 0.58985 (9) | 0.03172 (9) | 0.0129 (2) | |
| K3 | −0.27856 (10) | −0.21632 (9) | 0.42126 (9) | 0.0133 (2) | |
| N3 | −0.3585 (4) | −0.1085 (4) | 0.1198 (4) | 0.0150 (7) | |
| N4 | −0.3673 (5) | 0.3229 (4) | −0.0868 (4) | 0.0182 (8) | |
| N1 | −0.3641 (5) | 0.0960 (4) | 0.5568 (4) | 0.0157 (7) | |
| N2 | 0.0322 (5) | −0.0987 (5) | 0.2950 (5) | 0.0298 (10) | |
| N5 | 0.0203 (5) | 0.3068 (5) | 0.0908 (5) | 0.0336 (11) | |
| C6 | −0.3280 (5) | 0.4105 (4) | 0.3111 (4) | 0.0144 (8) | |
| C4 | −0.3348 (5) | 0.2756 (4) | 0.0224 (4) | 0.0127 (7) | |
| C5 | −0.0799 (5) | 0.2568 (5) | 0.1380 (5) | 0.0219 (9) | |
| C1 | −0.3329 (5) | 0.1282 (4) | 0.4402 (4) | 0.0125 (7) | |
| C3 | −0.3286 (5) | −0.0076 (4) | 0.1562 (4) | 0.0136 (8) | |
| C2 | −0.0739 (5) | 0.0069 (5) | 0.2682 (5) | 0.0206 (9) | |
| N6 | −0.3562 (5) | 0.5301 (4) | 0.3555 (4) | 0.0174 (8) | |
| C7 | −0.5434 (6) | 0.2691 (4) | 0.2568 (4) | 0.0166 (8) | |
| N7 | −0.6817 (5) | 0.3103 (4) | 0.2748 (4) | 0.0209 (8) | |
| O1 | −0.0067 (7) | −0.3954 (6) | 0.2344 (7) | 0.0609 (15) | 0.90 |
| O2 | −0.0141 (11) | −0.2434 (11) | 0.5544 (12) | 0.075 (3) | 0.60 |
| O3 | −0.0025 (13) | −0.4462 (11) | 0.4867 (14) | 0.070 (3) | 0.50 |
| H1 | 0.019 (9) | −0.488 (3) | 0.199 (6) | 0.05 (2)* | 0.90 |
| H2 | 0.007 (9) | −0.343 (6) | 0.157 (4) | 0.05 (2)* | 0.90 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mo1 | 0.0125 (2) | 0.0083 (2) | 0.0092 (2) | −0.00373 (15) | −0.00109 (14) | −0.00049 (14) |
| K4 | 0.0150 (5) | 0.0119 (5) | 0.0117 (5) | −0.0060 (4) | −0.0028 (4) | 0.0013 (4) |
| K1 | 0.0201 (5) | 0.0125 (4) | 0.0116 (5) | −0.0058 (4) | −0.0027 (4) | 0.0011 (3) |
| K2 | 0.0167 (5) | 0.0075 (4) | 0.0163 (5) | −0.0065 (4) | −0.0022 (4) | 0.0014 (4) |
| K3 | 0.0172 (5) | 0.0080 (4) | 0.0156 (5) | −0.0044 (4) | −0.0034 (4) | −0.0020 (4) |
| N3 | 0.0166 (18) | 0.0182 (17) | 0.0096 (16) | −0.0053 (14) | −0.0019 (13) | 0.0032 (13) |
| N4 | 0.0192 (19) | 0.0188 (18) | 0.0187 (19) | −0.0099 (15) | 0.0020 (15) | −0.0051 (14) |
| N1 | 0.0215 (19) | 0.0164 (17) | 0.0104 (17) | −0.0066 (14) | −0.0051 (14) | 0.0010 (13) |
| N2 | 0.020 (2) | 0.030 (2) | 0.037 (3) | −0.0057 (17) | −0.0057 (18) | 0.006 (2) |
| N5 | 0.018 (2) | 0.036 (3) | 0.045 (3) | −0.0082 (19) | −0.004 (2) | 0.012 (2) |
| C6 | 0.018 (2) | 0.0144 (18) | 0.0123 (19) | −0.0064 (15) | −0.0022 (15) | −0.0001 (14) |
| C4 | 0.019 (2) | 0.0074 (16) | 0.0137 (19) | −0.0076 (14) | −0.0029 (15) | 0.0011 (14) |
| C5 | 0.016 (2) | 0.016 (2) | 0.033 (3) | −0.0037 (16) | −0.0025 (18) | 0.0030 (17) |
| C1 | 0.0159 (19) | 0.0104 (17) | 0.0136 (19) | −0.0065 (14) | −0.0026 (15) | −0.0040 (14) |
| C3 | 0.0150 (19) | 0.0171 (19) | 0.0077 (17) | −0.0042 (15) | −0.0020 (14) | 0.0036 (14) |
| C2 | 0.018 (2) | 0.023 (2) | 0.023 (2) | −0.0085 (17) | −0.0036 (17) | 0.0039 (17) |
| N6 | 0.024 (2) | 0.0174 (18) | 0.0123 (18) | −0.0094 (15) | −0.0003 (14) | 0.0027 (13) |
| C7 | 0.027 (2) | 0.0129 (18) | 0.0099 (18) | −0.0064 (16) | −0.0014 (16) | −0.0054 (14) |
| N7 | 0.019 (2) | 0.0197 (19) | 0.026 (2) | −0.0070 (15) | −0.0041 (16) | −0.0097 (16) |
| O1 | 0.056 (4) | 0.035 (3) | 0.090 (4) | −0.013 (3) | −0.004 (3) | −0.006 (3) |
| O2 | 0.058 (6) | 0.070 (6) | 0.088 (7) | −0.008 (5) | −0.014 (5) | 0.015 (5) |
| O3 | 0.052 (6) | 0.054 (6) | 0.105 (9) | −0.024 (6) | −0.009 (6) | 0.022 (6) |
| Mo1—C2 | 2.120 (4) | K2—N4vii | 2.934 (4) |
| Mo1—C5 | 2.135 (4) | K2—N7vii | 3.096 (4) |
| Mo1—C1 | 2.150 (4) | K2—C4 | 3.109 (4) |
| Mo1—C4 | 2.156 (4) | K2—N4 | 3.134 (4) |
| Mo1—C6 | 2.160 (4) | K2—C6 | 3.150 (4) |
| Mo1—C3 | 2.164 (4) | K2—N6 | 3.181 (4) |
| Mo1—C7 | 2.198 (5) | K2—N5 | 3.188 (4) |
| K4—N1i | 2.836 (4) | K2—C5 | 3.229 (4) |
| K4—N2 | 2.888 (5) | K2—C4vii | 3.329 (4) |
| K4—N3ii | 2.948 (4) | K2—C7vii | 3.380 (4) |
| K4—N3iii | 2.983 (4) | K3—O2 | 2.767 (10) |
| K4—N7ii | 3.076 (4) | K3—N6viii | 2.788 (4) |
| K4—N4iii | 3.119 (4) | K3—O3 | 2.806 (11) |
| K4—N5 | 3.141 (4) | K3—O1 | 2.912 (6) |
| K4—C3iii | 3.185 (4) | K3—N1ix | 2.989 (4) |
| K4—C2 | 3.250 (4) | K3—N7ix | 3.039 (4) |
| K4—C4iii | 3.274 (4) | K3—N1 | 3.081 (4) |
| K4—C3ii | 3.317 (4) | K3—C1 | 3.093 (4) |
| K4—C7ii | 3.362 (4) | K3—C3 | 3.125 (4) |
| K1—N4iii | 2.783 (4) | K3—N3 | 3.140 (4) |
| K1—O3 | 2.888 (10) | K3—C2 | 3.339 (4) |
| K1—N2 | 2.900 (4) | K3—N2 | 3.344 (5) |
| K1—O2 | 2.921 (10) | N3—C3 | 1.140 (6) |
| K1—N7iv | 3.031 (4) | N4—C4 | 1.161 (6) |
| K1—N6i | 3.046 (4) | N1—C1 | 1.174 (5) |
| K1—N1i | 3.051 (4) | N2—C2 | 1.167 (6) |
| K1—N6iv | 3.051 (4) | N5—C5 | 1.161 (6) |
| K1—O1 | 3.075 (6) | C6—N6 | 1.154 (5) |
| K1—C6i | 3.200 (4) | C7—N7 | 1.154 (6) |
| K1—C1i | 3.210 (4) | O1—K2viii | 3.383 (6) |
| K1—C7iv | 3.362 (4) | O1—H1 | 0.89 (2) |
| K2—N3v | 2.819 (4) | O1—H2 | 0.89 (2) |
| K2—N5vi | 2.882 (5) | O3—O3x | 1.005 (18) |
| C2—Mo1—C5 | 74.20 (16) | C5—K2—C4vii | 129.62 (10) |
| C2—Mo1—C1 | 75.73 (16) | N3v—K2—C7vii | 88.06 (10) |
| C5—Mo1—C1 | 126.45 (17) | N5vi—K2—C7vii | 86.38 (12) |
| C2—Mo1—C4 | 125.11 (16) | N4vii—K2—C7vii | 68.44 (11) |
| C5—Mo1—C4 | 75.08 (17) | N7vii—K2—C7vii | 19.92 (11) |
| C1—Mo1—C4 | 155.91 (15) | C4—K2—C7vii | 95.04 (10) |
| C2—Mo1—C6 | 120.52 (17) | N4—K2—C7vii | 74.03 (10) |
| C5—Mo1—C6 | 75.93 (16) | C6—K2—C7vii | 142.50 (11) |
| C1—Mo1—C6 | 82.82 (14) | N6—K2—C7vii | 143.29 (11) |
| C4—Mo1—C6 | 93.98 (14) | N5—K2—C7vii | 133.68 (11) |
| C2—Mo1—C3 | 77.55 (16) | C5—K2—C7vii | 135.26 (11) |
| C5—Mo1—C3 | 122.98 (16) | C4vii—K2—C7vii | 48.32 (10) |
| C1—Mo1—C3 | 91.60 (14) | O2—K3—N6viii | 121.8 (2) |
| C4—Mo1—C3 | 82.69 (14) | O2—K3—O3 | 42.0 (3) |
| C6—Mo1—C3 | 158.53 (16) | N6viii—K3—O3 | 80.6 (2) |
| C2—Mo1—C7 | 144.39 (15) | O2—K3—O1 | 75.4 (3) |
| C5—Mo1—C7 | 141.38 (15) | N6viii—K3—O1 | 74.07 (13) |
| C1—Mo1—C7 | 77.75 (15) | O3—K3—O1 | 51.2 (3) |
| C4—Mo1—C7 | 78.21 (15) | O2—K3—N1ix | 144.9 (2) |
| C6—Mo1—C7 | 78.68 (15) | N6viii—K3—N1ix | 77.83 (11) |
| C3—Mo1—C7 | 79.88 (14) | O3—K3—N1ix | 148.6 (2) |
| C2—Mo1—K2 | 125.94 (11) | O1—K3—N1ix | 139.68 (15) |
| C5—Mo1—K2 | 51.79 (11) | O2—K3—N7ix | 66.5 (2) |
| C1—Mo1—K2 | 132.54 (9) | N6viii—K3—N7ix | 88.30 (11) |
| C4—Mo1—K2 | 48.64 (10) | O3—K3—N7ix | 69.5 (3) |
| C6—Mo1—K2 | 49.76 (10) | O1—K3—N7ix | 119.81 (15) |
| C3—Mo1—K2 | 131.31 (10) | N1ix—K3—N7ix | 87.22 (11) |
| C7—Mo1—K2 | 89.59 (10) | O2—K3—N1 | 76.9 (2) |
| C2—Mo1—K3 | 54.13 (11) | N6viii—K3—N1 | 151.78 (12) |
| C5—Mo1—K3 | 128.27 (11) | O3—K3—N1 | 118.3 (3) |
| C1—Mo1—K3 | 47.57 (9) | O1—K3—N1 | 133.85 (13) |
| C4—Mo1—K3 | 131.21 (10) | N1ix—K3—N1 | 75.93 (11) |
| C6—Mo1—K3 | 130.36 (11) | N7ix—K3—N1 | 80.28 (9) |
| C3—Mo1—K3 | 48.53 (10) | O2—K3—C1 | 83.5 (2) |
| C7—Mo1—K3 | 90.34 (10) | N6viii—K3—C1 | 154.61 (11) |
| K2—Mo1—K3 | 179.844 (19) | O3—K3—C1 | 124.7 (2) |
| N1i—K4—N2 | 74.36 (12) | O1—K3—C1 | 118.24 (13) |
| N1i—K4—N3ii | 79.64 (10) | N1ix—K3—C1 | 79.58 (10) |
| N2—K4—N3ii | 136.55 (11) | N7ix—K3—C1 | 102.07 (10) |
| N1i—K4—N3iii | 155.68 (12) | N1—K3—C1 | 21.93 (10) |
| N2—K4—N3iii | 128.12 (12) | O2—K3—C3 | 118.1 (2) |
| N3ii—K4—N3iii | 76.83 (11) | N6viii—K3—C3 | 104.25 (11) |
| N1i—K4—N7ii | 83.60 (11) | O3—K3—C3 | 129.1 (3) |
| N2—K4—N7ii | 120.85 (12) | O1—K3—C3 | 80.92 (15) |
| N3ii—K4—N7ii | 89.44 (11) | N1ix—K3—C3 | 78.63 (10) |
| N3iii—K4—N7ii | 90.10 (11) | N7ix—K3—C3 | 158.45 (10) |
| N1i—K4—N4iii | 88.28 (10) | N1—K3—C3 | 80.57 (10) |
| N2—K4—N4iii | 70.89 (11) | C1—K3—C3 | 59.65 (10) |
| N3ii—K4—N4iii | 74.16 (11) | O2—K3—N3 | 132.2 (2) |
| N3iii—K4—N4iii | 91.13 (11) | N6viii—K3—N3 | 83.31 (10) |
| N7ii—K4—N4iii | 162.80 (11) | O3—K3—N3 | 125.4 (3) |
| N1i—K4—N5 | 128.70 (12) | O1—K3—N3 | 74.17 (15) |
| N2—K4—N5 | 86.40 (12) | N1ix—K3—N3 | 74.35 (10) |
| N3ii—K4—N5 | 136.58 (11) | N7ix—K3—N3 | 160.97 (11) |
| N3iii—K4—N5 | 68.27 (11) | N1—K3—N3 | 99.33 (10) |
| N7ii—K4—N5 | 66.26 (12) | C1—K3—N3 | 79.57 (10) |
| N4iii—K4—N5 | 129.74 (12) | C3—K3—N3 | 20.96 (10) |
| N1i—K4—C3iii | 155.52 (11) | O2—K3—C2 | 69.3 (2) |
| N2—K4—C3iii | 111.36 (12) | N6viii—K3—C2 | 137.97 (11) |
| N3ii—K4—C3iii | 80.82 (10) | O3—K3—C2 | 93.7 (2) |
| N3iii—K4—C3iii | 20.96 (10) | O1—K3—C2 | 70.34 (13) |
| N7ii—K4—C3iii | 110.84 (11) | N1ix—K3—C2 | 117.51 (11) |
| N4iii—K4—C3iii | 72.25 (10) | N7ix—K3—C2 | 128.83 (11) |
| N5—K4—C3iii | 75.78 (11) | N1—K3—C2 | 65.60 (11) |
| N1i—K4—C2 | 88.58 (11) | C1—K3—C2 | 47.92 (11) |
| N2—K4—C2 | 20.85 (11) | C3—K3—C2 | 48.92 (11) |
| N3ii—K4—C2 | 157.13 (11) | N3—K3—C2 | 66.16 (10) |
| N3iii—K4—C2 | 115.65 (11) | O2—K3—N2 | 54.2 (2) |
| N7ii—K4—C2 | 108.80 (11) | N6viii—K3—N2 | 130.22 (11) |
| N4iii—K4—C2 | 86.05 (11) | O3—K3—N2 | 73.6 (2) |
| N5—K4—C2 | 65.55 (11) | O1—K3—N2 | 56.52 (13) |
| C3iii—K4—C2 | 104.29 (11) | N1ix—K3—N2 | 137.62 (10) |
| N1i—K4—C4iii | 109.02 (10) | N7ix—K3—N2 | 119.73 (11) |
| N2—K4—C4iii | 77.45 (11) | N1—K3—N2 | 77.35 (10) |
| N3ii—K4—C4iii | 78.98 (10) | C1—K3—N2 | 63.97 (10) |
| N3iii—K4—C4iii | 72.38 (10) | C3—K3—N2 | 64.95 (10) |
| N7ii—K4—C4iii | 160.72 (11) | N3—K3—N2 | 78.27 (10) |
| N4iii—K4—C4iii | 20.75 (10) | C2—K3—N2 | 20.11 (10) |
| N5—K4—C4iii | 112.42 (12) | C3—N3—K2viii | 154.0 (3) |
| C3iii—K4—C4iii | 52.41 (10) | C3—N3—K4xi | 98.7 (3) |
| C2—K4—C4iii | 86.57 (11) | K2viii—N3—K4xi | 106.90 (12) |
| N1i—K4—C3ii | 77.63 (10) | C3—N3—K4iii | 89.6 (3) |
| N2—K4—C3ii | 148.30 (11) | K2viii—N3—K4iii | 89.18 (11) |
| N3ii—K4—C3ii | 19.86 (10) | K4xi—N3—K4iii | 103.17 (11) |
| N3iii—K4—C3ii | 78.16 (9) | C3—N3—K3 | 78.8 (3) |
| N7ii—K4—C3ii | 69.59 (10) | K2viii—N3—K3 | 92.09 (10) |
| N4iii—K4—C3ii | 93.89 (10) | K4xi—N3—K3 | 99.76 (11) |
| N5—K4—C3ii | 123.26 (11) | K4iii—N3—K3 | 155.59 (14) |
| C3iii—K4—C3ii | 88.77 (10) | C4—N4—K1iii | 151.2 (3) |
| C2—K4—C3ii | 166.20 (10) | C4—N4—K2vii | 99.5 (3) |
| C4iii—K4—C3ii | 98.25 (10) | K1iii—N4—K2vii | 109.07 (13) |
| N1i—K4—C7ii | 80.29 (10) | C4—N4—K4iii | 87.2 (3) |
| N2—K4—C7ii | 136.66 (12) | K1iii—N4—K4iii | 84.27 (10) |
| N3ii—K4—C7ii | 69.42 (10) | K2vii—N4—K4iii | 99.88 (11) |
| N3iii—K4—C7ii | 85.77 (10) | C4—N4—K2 | 78.1 (3) |
| N7ii—K4—C7ii | 20.02 (10) | K1iii—N4—K2 | 97.92 (11) |
| N4iii—K4—C7ii | 143.19 (10) | K2vii—N4—K2 | 104.52 (11) |
| N5—K4—C7ii | 82.72 (12) | K4iii—N4—K2 | 153.20 (14) |
| C3iii—K4—C7ii | 106.31 (10) | C1—N1—K4i | 154.3 (3) |
| C2—K4—C7ii | 128.06 (11) | C1—N1—K3ix | 99.3 (3) |
| C4iii—K4—C7ii | 144.98 (11) | K4i—N1—K3ix | 106.16 (12) |
| C3ii—K4—C7ii | 49.57 (10) | C1—N1—K1i | 86.9 (3) |
| N4iii—K1—O3 | 126.5 (3) | K4i—N1—K1i | 84.65 (10) |
| N4iii—K1—N2 | 75.70 (12) | K3ix—N1—K1i | 102.10 (11) |
| O3—K1—N2 | 79.8 (2) | C1—N1—K3 | 79.6 (3) |
| N4iii—K1—O2 | 132.7 (2) | K4i—N1—K3 | 97.05 (11) |
| O3—K1—O2 | 40.3 (3) | K3ix—N1—K3 | 104.07 (11) |
| N2—K1—O2 | 58.2 (2) | K1i—N1—K3 | 152.14 (14) |
| N4iii—K1—N7iv | 83.94 (11) | C2—N2—K4 | 97.4 (3) |
| O3—K1—N7iv | 72.6 (3) | C2—N2—K1 | 176.0 (4) |
| N2—K1—N7iv | 124.93 (12) | K4—N2—K1 | 86.55 (12) |
| O2—K1—N7iv | 112.8 (2) | C2—N2—K3 | 79.7 (3) |
| N4iii—K1—N6i | 151.13 (12) | K4—N2—K3 | 176.65 (16) |
| O3—K1—N6i | 73.8 (3) | K1—N2—K3 | 96.37 (12) |
| N2—K1—N6i | 132.09 (12) | C5—N5—K2vi | 176.1 (4) |
| O2—K1—N6i | 76.2 (2) | C5—N5—K4 | 91.7 (3) |
| N7iv—K1—N6i | 83.89 (11) | K2vi—N5—K4 | 85.04 (11) |
| N4iii—K1—N1i | 90.63 (10) | C5—N5—K2 | 81.6 (3) |
| O3—K1—N1i | 124.6 (3) | K2vi—N5—K2 | 101.74 (12) |
| N2—K1—N1i | 71.04 (12) | K4—N5—K2 | 173.03 (16) |
| O2—K1—N1i | 84.5 (2) | N6—C6—Mo1 | 178.8 (4) |
| N7iv—K1—N1i | 160.62 (11) | N6—C6—K2 | 81.0 (3) |
| N6i—K1—N1i | 92.27 (10) | Mo1—C6—K2 | 98.68 (14) |
| N4iii—K1—N6iv | 79.25 (11) | N6—C6—K1i | 71.9 (3) |
| O3—K1—N6iv | 143.8 (2) | Mo1—C6—K1i | 108.80 (14) |
| N2—K1—N6iv | 135.46 (11) | K2—C6—K1i | 146.00 (14) |
| O2—K1—N6iv | 141.7 (2) | N6—C6—K1xii | 62.6 (3) |
| N7iv—K1—N6iv | 87.65 (11) | Mo1—C6—K1xii | 116.23 (15) |
| N6i—K1—N6iv | 74.18 (11) | K2—C6—K1xii | 90.47 (10) |
| N1i—K1—N6iv | 73.05 (10) | K1i—C6—K1xii | 94.81 (10) |
| N4iii—K1—O1 | 77.78 (15) | N4—C4—Mo1 | 178.7 (4) |
| O3—K1—O1 | 48.9 (3) | N4—C4—K2 | 80.5 (3) |
| N2—K1—O1 | 59.89 (13) | Mo1—C4—K2 | 100.01 (13) |
| O2—K1—O1 | 70.8 (3) | N4—C4—K4iii | 72.1 (3) |
| N7iv—K1—O1 | 66.03 (12) | Mo1—C4—K4iii | 107.93 (13) |
| N6i—K1—O1 | 120.18 (14) | K2—C4—K4iii | 144.67 (13) |
| N1i—K1—O1 | 130.92 (12) | N4—C4—K2vii | 60.4 (3) |
| N6iv—K1—O1 | 146.53 (13) | Mo1—C4—K2vii | 118.33 (15) |
| N4iii—K1—C6i | 155.00 (11) | K2—C4—K2vii | 96.36 (10) |
| O3—K1—C6i | 78.4 (3) | K4iii—C4—K2vii | 89.15 (10) |
| N2—K1—C6i | 115.01 (12) | N5—C5—Mo1 | 174.1 (4) |
| O2—K1—C6i | 66.0 (2) | N5—C5—K2 | 77.6 (3) |
| N7iv—K1—C6i | 104.87 (11) | Mo1—C5—K2 | 96.91 (15) |
| N6i—K1—C6i | 21.12 (10) | N5—C5—K4 | 68.2 (3) |
| N1i—K1—C6i | 73.26 (10) | Mo1—C5—K4 | 117.19 (16) |
| N6iv—K1—C6i | 77.82 (10) | K2—C5—K4 | 145.76 (14) |
| O1—K1—C6i | 127.22 (14) | N1—C1—Mo1 | 179.0 (3) |
| N4iii—K1—C1i | 112.02 (11) | N1—C1—K3 | 78.5 (3) |
| O3—K1—C1i | 108.7 (3) | Mo1—C1—K3 | 101.55 (13) |
| N2—K1—C1i | 78.95 (12) | N1—C1—K1i | 71.7 (3) |
| O2—K1—C1i | 71.3 (2) | Mo1—C1—K1i | 108.74 (13) |
| N7iv—K1—C1i | 154.97 (11) | K3—C1—K1i | 141.57 (14) |
| N6i—K1—C1i | 72.96 (10) | N1—C1—K3ix | 60.7 (3) |
| N1i—K1—C1i | 21.43 (10) | Mo1—C1—K3ix | 118.36 (15) |
| N6iv—K1—C1i | 77.16 (10) | K3—C1—K3ix | 95.18 (10) |
| O1—K1—C1i | 134.42 (12) | K1i—C1—K3ix | 90.83 (9) |
| C6i—K1—C1i | 52.82 (10) | N3—C3—Mo1 | 178.1 (4) |
| N4iii—K1—C7iv | 78.81 (10) | N3—C3—K3 | 80.3 (3) |
| O3—K1—C7iv | 90.8 (2) | Mo1—C3—K3 | 100.21 (13) |
| N2—K1—C7iv | 139.24 (12) | N3—C3—K4iii | 69.5 (3) |
| O2—K1—C7iv | 129.9 (2) | Mo1—C3—K4iii | 110.74 (14) |
| N7iv—K1—C7iv | 19.95 (11) | K3—C3—K4iii | 143.04 (14) |
| N6i—K1—C7iv | 80.85 (10) | N3—C3—K4xi | 61.5 (3) |
| N1i—K1—C7iv | 140.67 (11) | Mo1—C3—K4xi | 116.62 (15) |
| N6iv—K1—C7iv | 67.80 (10) | K3—C3—K4xi | 92.56 (10) |
| O1—K1—C7iv | 84.04 (12) | K4iii—C3—K4xi | 91.23 (10) |
| C6i—K1—C7iv | 101.40 (10) | N2—C2—Mo1 | 175.1 (4) |
| C1i—K1—C7iv | 140.79 (11) | N2—C2—K4 | 61.8 (3) |
| N3v—K2—N5vi | 74.20 (12) | Mo1—C2—K4 | 123.11 (17) |
| N3v—K2—N4vii | 79.00 (11) | N2—C2—K3 | 80.2 (3) |
| N5vi—K2—N4vii | 143.65 (11) | Mo1—C2—K3 | 94.90 (14) |
| N3v—K2—N7vii | 92.82 (10) | K4—C2—K3 | 141.94 (14) |
| N5vi—K2—N7vii | 69.19 (12) | C6—N6—K3v | 154.2 (3) |
| N4vii—K2—N7vii | 88.33 (11) | C6—N6—K1i | 87.0 (3) |
| N3v—K2—C4 | 154.84 (11) | K3v—N6—K1i | 93.00 (11) |
| N5vi—K2—C4 | 130.86 (12) | C6—N6—K1xii | 97.7 (3) |
| N4vii—K2—C4 | 78.98 (11) | K3v—N6—K1xii | 107.02 (12) |
| N7vii—K2—C4 | 98.55 (10) | K1i—N6—K1xii | 105.82 (11) |
| N3v—K2—N4 | 152.82 (11) | C6—N6—K2 | 78.0 (3) |
| N5vi—K2—N4 | 123.51 (12) | K3v—N6—K2 | 91.82 (10) |
| N4vii—K2—N4 | 75.48 (11) | K1i—N6—K2 | 154.44 (14) |
| N7vii—K2—N4 | 77.34 (10) | K1xii—N6—K2 | 96.69 (11) |
| C4—K2—N4 | 21.43 (10) | N7—C7—Mo1 | 178.9 (4) |
| N3v—K2—C6 | 103.06 (11) | N7—C7—K1xii | 63.6 (2) |
| N5vi—K2—C6 | 131.04 (12) | Mo1—C7—K1xii | 116.63 (15) |
| N4vii—K2—C6 | 78.58 (11) | N7—C7—K4xi | 65.9 (3) |
| N7vii—K2—C6 | 156.93 (10) | Mo1—C7—K4xi | 113.90 (14) |
| C4—K2—C6 | 60.55 (10) | K1xii—C7—K4xi | 129.43 (15) |
| N4—K2—C6 | 81.01 (10) | N7—C7—K2vii | 66.0 (3) |
| N3v—K2—N6 | 82.07 (9) | Mo1—C7—K2vii | 115.03 (15) |
| N5vi—K2—N6 | 123.91 (12) | K1xii—C7—K2vii | 83.05 (10) |
| N4vii—K2—N6 | 74.98 (11) | K4xi—C7—K2vii | 74.38 (9) |
| N7vii—K2—N6 | 163.17 (11) | N7—C7—K3ix | 62.5 (3) |
| C4—K2—N6 | 80.61 (10) | Mo1—C7—K3ix | 116.39 (16) |
| N4—K2—N6 | 100.02 (10) | K1xii—C7—K3ix | 77.65 (9) |
| C6—K2—N6 | 21.00 (10) | K4xi—C7—K3ix | 82.09 (10) |
| N3v—K2—N5 | 127.59 (12) | K2vii—C7—K3ix | 128.45 (14) |
| N5vi—K2—N5 | 78.26 (12) | C7—N7—K1xii | 96.4 (3) |
| N4vii—K2—N5 | 138.08 (11) | C7—N7—K3ix | 97.8 (3) |
| N7vii—K2—N5 | 117.52 (11) | K1xii—N7—K3ix | 88.49 (10) |
| C4—K2—N5 | 65.63 (11) | C7—N7—K4xi | 94.1 (3) |
| N4—K2—N5 | 78.79 (11) | K1xii—N7—K4xi | 169.07 (15) |
| C6—K2—N5 | 65.05 (11) | K3ix—N7—K4xi | 93.01 (11) |
| N6—K2—N5 | 77.64 (11) | C7—N7—K2vii | 94.0 (3) |
| N3v—K2—C5 | 136.31 (12) | K1xii—N7—K2vii | 93.66 (11) |
| N5vi—K2—C5 | 99.08 (12) | K3ix—N7—K2vii | 167.66 (15) |
| N4vii—K2—C5 | 117.27 (11) | K4xi—N7—K2vii | 82.64 (10) |
| N7vii—K2—C5 | 125.79 (11) | K3—O1—K1 | 102.27 (19) |
| C4—K2—C5 | 48.67 (11) | K3—O1—K2viii | 85.71 (15) |
| N4—K2—C5 | 66.00 (11) | K1—O1—K2viii | 169.2 (2) |
| C6—K2—C5 | 48.91 (11) | K3—O1—H1 | 133 (5) |
| N6—K2—C5 | 65.90 (11) | K1—O1—H1 | 109 (5) |
| N5—K2—C5 | 20.83 (10) | K2viii—O1—H1 | 70 (5) |
| N3v—K2—C4vii | 79.86 (10) | K3—O1—H2 | 110 (4) |
| N5vi—K2—C4vii | 128.22 (11) | K1—O1—H2 | 97 (5) |
| N4vii—K2—C4vii | 20.13 (10) | K2viii—O1—H2 | 73 (5) |
| N7vii—K2—C4vii | 68.23 (10) | H1—O1—H2 | 100 (3) |
| C4—K2—C4vii | 83.64 (10) | K3—O2—K1 | 110.1 (4) |
| N4—K2—C4vii | 72.96 (10) | O3x—O3—K3 | 124.8 (14) |
| C6—K2—C4vii | 97.92 (10) | O3x—O3—K1 | 121.3 (14) |
| N6—K2—C4vii | 95.04 (10) | K3—O3—K1 | 109.9 (3) |
| N5—K2—C4vii | 149.11 (11) |
| Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) −x, −y, −z; (iv) x+1, y−1, z; (v) x, y+1, z; (vi) −x, −y+1, −z; (vii) −x−1, −y+1, −z; (viii) x, y−1, z; (ix) −x−1, −y, −z+1; (x) −x, −y−1, −z+1; (xi) x−1, y, z; (xii) x−1, y+1, z. |
The present research was supported in part by a Grant-in-Aid for Young Scientists (S) from JSPS, a grant for the Global COE Program, Chemistry Innovation through Cooperation of Science and Engineering, the Photon Frontier Network Program from MEXT, Japan, the Kurata Memorial Hitachi Science and Technology Foundation, and the Inamori Foundation. YT is grateful to JSPS Research Fellowships for Young Scientists. A part of this work was conducted at the Center for Nano Lithography & Analysis at the University of Tokyo, supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.
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In the field of molecule-based magnets, cyano-bridged metal assemblies have been much studied to demonstrate novel functionalities. Octacyanometalate-based materials show interesting functionalities such as photomagnetism (Arimoto et al., 2003; Catala et al., 2005; Ohkoshi et al., 2008) and chemically sensitive magnetism (Ohkoshi et al., 2007). As a versatile class of building blocks, a heptacyanomolybdate ion [MoIII(CN)7]4- is also attractive because this metal complex can adopt various spatial configurations, depending on the chemical environment, pentagonal bipyramid (D5 h) and capped trigonal prism (C2v) (Rossman et al., 1973; Larionova et al., 2004). Although the coordination geometry of pentagonal bipyramid (D5 h) has been observed with the mixed salt NaIKI 3[Mo(CN)7]2H2O, that of capped trigonal prism (C2 v) has not been reported (Hursthouse et al., 1980, Drew et al., 1977). In this paper, we report the crystal structure of KI4[MoIII(CN)7]2H2O with capped trigonal prism (C2v) symmetry, which has the asymmetric unit of one [MoIII(CN)7]4- anion, four K+ cations, and two water molecules distributed over three sites with site occupation factors (s.o.f's) of 0.90, 0.60 and 0.50. (Fig. 1). The synthesis and the spectral information of the title compound as been reported by Young (1932) and Rossman et al., (1973).