Acta Cryst. (2007). E63, m1730 [ doi:10.1107/S1600536807022921 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-iodido-[iodidocadmium(II)]-bis(-4-methylpyridine N-oxide)]In the title complex, [CdI2(C6H7NO)]n, the CdII ion exhibits a trigonal-bipyramidal coordination geometry [Cd-O = 2.272 (4) Å and Cd-I = 2.7054 (7)-2.8049 (8) Å], with iodide anions and 4-methylpyridine N-oxide ligands acting as bridging groups to form a one-dimensional chain structure.
Cd(ClO4)2.6H2O (0.2724 g, 0.649 mmol), 4-methylpyridine N-oxide (0.0793 g, 0.727 mmol) and NaI (0.2417 g, 1.61 mmol) were dissolved in 10 ml H2O, respectively, and then the three solutions were mixed together. The colorless single crystals (I) were obtained after allowing the mixed solution to stand at room temperature for two weeks.
The H atoms were placed in calculated positions and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2eq(C) for pyridine ring; C—H = 0.96 Å, Uiso(H) = 1.5eq(C) for the methyl group.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
![[Figure 1]](./lh2387fig1thm.gif)
| Fig. 1. Part of the structure of (I) showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) -x, -y + 2, -z + 2; (ii) -x + 1, -y + 2, -z + 2]. |
![[Figure 2]](./lh2387fig2thm.gif)
| Fig. 2. Part of the crystal structure of (I). Dashed lines indicate weak C—H···I interactions. |
| [CdI2(C6H7NO)] | Z = 2 |
| Mr = 475.33 | F(000) = 424 |
| Triclinic, P1 | Dx = 2.880 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.0584 (16) Å | Cell parameters from 1365 reflections |
| b = 8.4025 (19) Å | θ = 2.6–26.8° |
| c = 9.875 (2) Å | µ = 7.58 mm−1 |
| α = 102.633 (3)° | T = 293 K |
| β = 96.050 (3)° | Block, colorless |
| γ = 103.510 (3)° | 0.09 × 0.08 × 0.07 mm |
| V = 548.1 (2) Å3 |
| Bruker SMART APEX CCD diffractometer | 2147 independent reflections |
| Radiation source: fine-focus sealed tube | 1839 reflections with I > 2σ(I) |
| graphite | Rint = 0.017 |
| φ and ω scans | θmax = 26.2°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.549, Tmax = 0.619 | k = −8→10 |
| 3046 measured reflections | l = −12→10 |
| 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)] = 0.030 | H-atom parameters constrained |
| wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0308P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max = 0.037 |
| 2147 reflections | Δρmax = 0.85 e Å−3 |
| 102 parameters | Δρmin = −0.89 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0063 (5) |
| [CdI2(C6H7NO)] | γ = 103.510 (3)° |
| Mr = 475.33 | V = 548.1 (2) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.0584 (16) Å | Mo Kα radiation |
| b = 8.4025 (19) Å | µ = 7.58 mm−1 |
| c = 9.875 (2) Å | T = 293 K |
| α = 102.633 (3)° | 0.09 × 0.08 × 0.07 mm |
| β = 96.050 (3)° |
| Bruker SMART APEX CCD diffractometer | 2147 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1839 reflections with I > 2σ(I) |
| Tmin = 0.549, Tmax = 0.619 | Rint = 0.017 |
| 3046 measured reflections | θmax = 26.2° |
| R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
| wR(F2) = 0.070 | Δρmax = 0.85 e Å−3 |
| S = 1.02 | Δρmin = −0.89 e Å−3 |
| 2147 reflections | Absolute structure: ? |
| 102 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 | ||
| Cd1 | 0.25296 (6) | 0.96122 (5) | 1.07178 (4) | 0.03312 (14) | |
| I1 | 0.12264 (5) | 1.25617 (5) | 1.10555 (4) | 0.03973 (14) | |
| I2 | 0.31135 (7) | 0.81337 (6) | 1.28439 (4) | 0.05230 (16) | |
| C6 | 0.1724 (11) | 0.2298 (9) | 0.5226 (7) | 0.0588 (19) | |
| H6A | 0.1267 | 0.2389 | 0.4302 | 0.088* | |
| H6B | 0.0671 | 0.1605 | 0.5548 | 0.088* | |
| H6C | 0.2813 | 0.1795 | 0.5192 | 0.088* | |
| N1 | 0.3549 (6) | 0.7153 (6) | 0.8070 (5) | 0.0322 (10) | |
| C4 | 0.2630 (9) | 0.4203 (8) | 0.7651 (6) | 0.0419 (14) | |
| H4 | 0.2387 | 0.3249 | 0.8005 | 0.050* | |
| O1 | 0.4163 (6) | 0.8687 (5) | 0.8971 (4) | 0.0409 (10) | |
| C1 | 0.3308 (9) | 0.7026 (8) | 0.6688 (6) | 0.0438 (14) | |
| H1 | 0.3538 | 0.7997 | 0.6357 | 0.053* | |
| C5 | 0.3229 (9) | 0.5765 (8) | 0.8557 (6) | 0.0419 (14) | |
| H5 | 0.3418 | 0.5869 | 0.9522 | 0.050* | |
| C2 | 0.2719 (9) | 0.5459 (9) | 0.5757 (6) | 0.0475 (16) | |
| H2 | 0.2549 | 0.5384 | 0.4796 | 0.057* | |
| C3 | 0.2378 (9) | 0.4012 (8) | 0.6209 (6) | 0.0397 (14) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cd1 | 0.0310 (2) | 0.0323 (2) | 0.0372 (2) | 0.01002 (18) | 0.00636 (17) | 0.00883 (17) |
| I1 | 0.0335 (2) | 0.0305 (2) | 0.0513 (3) | 0.00987 (16) | −0.00021 (17) | 0.00418 (17) |
| I2 | 0.0631 (3) | 0.0504 (3) | 0.0487 (3) | 0.0166 (2) | 0.0047 (2) | 0.0239 (2) |
| C6 | 0.070 (5) | 0.042 (4) | 0.051 (4) | 0.004 (4) | 0.014 (4) | −0.005 (3) |
| N1 | 0.030 (2) | 0.025 (2) | 0.037 (3) | 0.0046 (19) | 0.0080 (19) | 0.001 (2) |
| C4 | 0.050 (4) | 0.029 (3) | 0.050 (4) | 0.013 (3) | 0.011 (3) | 0.011 (3) |
| O1 | 0.035 (2) | 0.033 (2) | 0.047 (2) | 0.0046 (17) | 0.0123 (18) | −0.0046 (18) |
| C1 | 0.053 (4) | 0.038 (4) | 0.041 (3) | 0.010 (3) | 0.008 (3) | 0.013 (3) |
| C5 | 0.046 (4) | 0.043 (4) | 0.037 (3) | 0.012 (3) | 0.006 (3) | 0.010 (3) |
| C2 | 0.052 (4) | 0.049 (4) | 0.038 (3) | 0.010 (3) | 0.005 (3) | 0.010 (3) |
| C3 | 0.039 (3) | 0.039 (4) | 0.037 (3) | 0.007 (3) | 0.011 (3) | 0.005 (3) |
| Cd1—O1 | 2.272 (4) | N1—C5 | 1.337 (8) |
| Cd1—O1i | 2.384 (4) | N1—O1 | 1.340 (5) |
| Cd1—I2 | 2.7054 (7) | C4—C5 | 1.360 (8) |
| Cd1—I1 | 2.8049 (8) | C4—C3 | 1.385 (8) |
| Cd1—I1ii | 2.9650 (7) | C4—H4 | 0.9300 |
| I1—Cd1ii | 2.9650 (7) | O1—Cd1i | 2.384 (4) |
| C6—C3 | 1.487 (8) | C1—C2 | 1.374 (9) |
| C6—H6A | 0.9600 | C1—H1 | 0.9300 |
| C6—H6B | 0.9600 | C5—H5 | 0.9300 |
| C6—H6C | 0.9600 | C2—C3 | 1.364 (9) |
| N1—C1 | 1.335 (7) | C2—H2 | 0.9300 |
| O1—Cd1—O1i | 67.55 (15) | C5—N1—O1 | 120.0 (5) |
| O1—Cd1—I2 | 109.61 (11) | C5—C4—C3 | 121.0 (6) |
| O1i—Cd1—I2 | 96.51 (11) | C5—C4—H4 | 119.5 |
| O1—Cd1—I1 | 124.55 (11) | C3—C4—H4 | 119.5 |
| O1i—Cd1—I1 | 88.89 (10) | N1—O1—Cd1 | 123.9 (3) |
| I2—Cd1—I1 | 122.90 (2) | N1—O1—Cd1i | 121.8 (3) |
| O1—Cd1—I1ii | 88.83 (10) | Cd1—O1—Cd1i | 112.45 (15) |
| O1i—Cd1—I1ii | 152.48 (9) | N1—C1—C2 | 119.9 (6) |
| I2—Cd1—I1ii | 104.94 (2) | N1—C1—H1 | 120.1 |
| I1—Cd1—I1ii | 93.61 (2) | C2—C1—H1 | 120.1 |
| Cd1—I1—Cd1ii | 86.39 (2) | N1—C5—C4 | 120.5 (5) |
| C3—C6—H6A | 109.5 | N1—C5—H5 | 119.8 |
| C3—C6—H6B | 109.5 | C4—C5—H5 | 119.8 |
| H6A—C6—H6B | 109.5 | C3—C2—C1 | 121.5 (6) |
| C3—C6—H6C | 109.5 | C3—C2—H2 | 119.3 |
| H6A—C6—H6C | 109.5 | C1—C2—H2 | 119.3 |
| H6B—C6—H6C | 109.5 | C2—C3—C4 | 116.7 (6) |
| C1—N1—C5 | 120.5 (5) | C2—C3—C6 | 122.7 (6) |
| C1—N1—O1 | 119.4 (5) | C4—C3—C6 | 120.6 (6) |
| O1—Cd1—I1—Cd1ii | 91.06 (12) | I2—Cd1—O1—Cd1i | −89.03 (17) |
| O1i—Cd1—I1—Cd1ii | 152.57 (10) | I1—Cd1—O1—Cd1i | 71.94 (19) |
| I2—Cd1—I1—Cd1ii | −110.39 (3) | I1ii—Cd1—O1—Cd1i | 165.52 (16) |
| I1ii—Cd1—I1—Cd1ii | 0.0 | C5—N1—C1—C2 | 0.3 (9) |
| C1—N1—O1—Cd1 | 125.4 (5) | O1—N1—C1—C2 | 178.6 (5) |
| C5—N1—O1—Cd1 | −56.2 (6) | C1—N1—C5—C4 | −0.8 (9) |
| C1—N1—O1—Cd1i | −71.6 (6) | O1—N1—C5—C4 | −179.2 (5) |
| C5—N1—O1—Cd1i | 106.8 (5) | C3—C4—C5—N1 | 1.3 (10) |
| O1i—Cd1—O1—N1 | 164.4 (5) | N1—C1—C2—C3 | −0.3 (10) |
| I2—Cd1—O1—N1 | 75.4 (4) | C1—C2—C3—C4 | 0.8 (10) |
| I1—Cd1—O1—N1 | −123.6 (4) | C1—C2—C3—C6 | 179.5 (6) |
| I1ii—Cd1—O1—N1 | −30.1 (4) | C5—C4—C3—C2 | −1.3 (9) |
| O1i—Cd1—O1—Cd1i | 0.0 | C5—C4—C3—C6 | 179.9 (6) |
| Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x, −y+2, −z+2. |
The authors thank the Natural Science Foundation of Shandong Province of China (grant No. Y2005B25).
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Shi, J.-M., Liu, Z., Wu, C.-J., Xu, H.-Y. & Liu, L.-D. (2006). J. Coord. Chem. 59, 1883–1889.
Complexes containing Cd(II) are very common and useful, and they have played an important role in functional materials, especially in the area of optics (Pecaut et al., 1993; Selvasekarapandian et al., 1997). In published work most CdII ions assume octahedron geometry with six coordinated atoms (Shi et al., 2006), and Cd(II) complexes with coordination number five are limited (Reger et al., 2002). We report here a novel one-dimensional Cd(II) complex (I) with five coordinated atoms.
The asymmetric unit and symmetry-related fragments of (I) are shown in Fig. 1. Atom Cd1 is in a distorted trigonal-bipyramidal CdO2I3 coordination geometry (Table 1). Atom I1 acts as a bridging ligand coordinated two CdII ions with a separation of 3.9511 (11) Å, which creates a four-membered ring with the four atoms strictly coplanar by virtue of the crystallographic inversion center which is in the middle of the four-membered ring. A neutral 4-methylpyridine N-oxide group also acts as bridging ligand with a pair of CdII ions having a separation of 3.8705 (11) Å also leading to the formation of a four-membered ring with the four atoms strictly coplanar by virtue of the crystallographic inversion center which is also at the middle of this four-membered ring. The dihedral angle of the two planes is 56.99 °. The two kinds of four-membered rings connect alternately, leading to the formation of a one-dimensional zigzag chain along the a axis as shown in Fig. 2. There is one weak interchain C—H···I interaction [H6A···I1(x, -1 + y, -1 + z) = 3.24 Å; C6—H6A···I1(x, -1 + y, -1 + z) = 160°. The chain structure in (I) is very similar to that of the complex {[Cd(µ-I)(µ-ONC5H5)]I}n (where ONC5H5 is pyridine N-oxide) (Sawitzki & Schnering, 1974), but the crystal system and space groups of the two crystals are different and probably attributed to the minor difference of the methyl substitution.