Acta Cryst. (2010). E66, m1486 [ doi:10.1107/S1600536810043205 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,N')copper(I)]-![[mu]](/logos/entities/mu_rmgif.gif)
2-iodido]The solvothermal reaction of copper(I) iodide and 1,10-phenanthroline (phen) in ethanol yielded the title polymeric compound, [CuI(C12H8N2)]n. The asymmmetric unit comprises one Cu+ cation, one I- anion and one phen ligand. Each Cu+ cation is in a distorted tetrahedral coordination by two iodide anions and two N atoms from a bidentate chelating phen ligand. The Cu+ cations are bridged through the iodide anions, leading to a zigzag chain structure extending parallel to [100]. There are ![[pi]](/logos/entities/pi_rmgif.gif)
- interactions among adjacent phen ligands of one chain [centroid-centroid distance = 3.693 (3) Å].
All chemicals were obtained from commercial sources and were used as received. The title compound was handily synthesized by a solvothermal reaction from CuI and phen. A mixture of CuI (76 mg, 0.4 mmol) and phen.H2O (80 mg, 0.4 mmol) in 12 mL alcohol was put into a Parr Teflon-lined autoclave (23 mL) and heated at 393 K for 3 days. After cooling down to room temperature, yellow crystals of compound I were obtained.
The structure was solved using direct methods and refined by full-matrix least-squares techniques. All non-hydrogen atoms were assigned anisotropic displacement parameters in the refinement. All hydrogen atoms were added at calculated positions and refined using a riding model. (Sheldrick, 2008).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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).
![[Figure 1]](./kp2280fig1thm.gif)
| Fig. 1. Structure and labelling of the title compound, with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii. Symmetry code A: x - 1, y, z. |
![[Figure 2]](./kp2280fig2thm.gif)
| Fig. 2. The chain structure constructed from Cu(phen)I unit. |
![[Figure 3]](./kp2280fig3thm.gif)
| Fig. 3. The packing diagram viewed along the a-direction. |
| [CuI(C12H8N2)] | F(000) = 704 |
| Mr = 370.64 | Dx = 2.213 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71075 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 2969 reflections |
| a = 4.1664 (5) Å | θ = 2.1–27.5° |
| b = 10.4621 (11) Å | µ = 4.71 mm−1 |
| c = 25.518 (4) Å | T = 293 K |
| V = 1112.3 (2) Å3 | Prism, yellow |
| Z = 4 | 0.35 × 0.10 × 0.05 mm |
| Rigaku R-AXIS RAPID diffractometer | 2567 independent reflections |
| Radiation source: fine-focus sealed tube | 2380 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| Detector resolution: 14.6306 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
| CCD_Profile_fitting scans | h = −5→5 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −13→13 |
| Tmin = 0.290, Tmax = 0.799 | l = −33→31 |
| 8582 measured reflections |
| 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)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.0192P)2 + 0.4704P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.12 | (Δ/σ)max = 0.001 |
| 2567 reflections | Δρmax = 0.94 e Å−3 |
| 145 parameters | Δρmin = −0.53 e Å−3 |
| 0 restraints | Absolute structure: Flack (1983), 1020 Friedel pairs? |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.05 (3) |
| [CuI(C12H8N2)] | V = 1112.3 (2) Å3 |
| Mr = 370.64 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 4.1664 (5) Å | µ = 4.71 mm−1 |
| b = 10.4621 (11) Å | T = 293 K |
| c = 25.518 (4) Å | 0.35 × 0.10 × 0.05 mm |
| Rigaku R-AXIS RAPID diffractometer | 2567 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2380 reflections with I > 2σ(I) |
| Tmin = 0.290, Tmax = 0.799 | Rint = 0.027 |
| 8582 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.056 | Δρmax = 0.94 e Å−3 |
| S = 1.12 | Δρmin = −0.53 e Å−3 |
| 2567 reflections | Absolute structure: Flack (1983), 1020 Friedel pairs? |
| 145 parameters | Flack parameter: 0.05 (3) |
| 0 restraints |
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 | ||
| I1 | 0.66039 (6) | 0.42090 (2) | 0.117804 (11) | 0.03947 (8) | |
| Cu1 | 0.16241 (14) | 0.27290 (4) | 0.12007 (2) | 0.03758 (12) | |
| N1 | 0.3102 (9) | 0.1092 (3) | 0.07823 (11) | 0.0338 (7) | |
| N2 | −0.0053 (9) | 0.1283 (3) | 0.17018 (13) | 0.0341 (7) | |
| C5 | 0.2334 (9) | −0.0008 (4) | 0.10317 (14) | 0.0315 (9) | |
| C12 | −0.1751 (12) | 0.1378 (4) | 0.21386 (15) | 0.0436 (10) | |
| H12 | −0.2174 | 0.2191 | 0.2269 | 0.052* | |
| C9 | 0.0515 (10) | 0.0084 (4) | 0.15161 (15) | 0.0315 (9) | |
| C4 | 0.3219 (12) | −0.1225 (4) | 0.08441 (16) | 0.0420 (10) | |
| C1 | 0.4834 (11) | 0.1005 (5) | 0.03491 (16) | 0.0448 (11) | |
| H1 | 0.5378 | 0.1752 | 0.0173 | 0.054* | |
| C8 | −0.0525 (10) | −0.1027 (4) | 0.17715 (17) | 0.0419 (11) | |
| C10 | −0.2305 (11) | −0.0865 (5) | 0.22338 (17) | 0.0536 (12) | |
| H10 | −0.3048 | −0.1575 | 0.2417 | 0.064* | |
| C6 | 0.2110 (14) | −0.2340 (4) | 0.1123 (2) | 0.0557 (14) | |
| H6 | 0.2677 | −0.3146 | 0.1000 | 0.067* | |
| C11 | −0.2940 (12) | 0.0332 (5) | 0.24137 (17) | 0.0532 (12) | |
| H11 | −0.4150 | 0.0450 | 0.2716 | 0.064* | |
| C3 | 0.5059 (13) | −0.1268 (5) | 0.03889 (19) | 0.0519 (13) | |
| H3 | 0.5720 | −0.2050 | 0.0254 | 0.062* | |
| C7 | 0.0286 (14) | −0.2250 (4) | 0.1555 (2) | 0.0546 (14) | |
| H7 | −0.0462 | −0.2990 | 0.1715 | 0.065* | |
| C2 | 0.5884 (12) | −0.0168 (5) | 0.01436 (18) | 0.0546 (14) | |
| H2 | 0.7135 | −0.0189 | −0.0158 | 0.066* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| I1 | 0.02550 (13) | 0.02861 (12) | 0.06429 (16) | 0.00102 (12) | 0.00327 (14) | 0.00180 (12) |
| Cu1 | 0.0322 (3) | 0.0280 (2) | 0.0525 (3) | 0.0003 (2) | 0.0052 (3) | 0.0017 (2) |
| N1 | 0.0326 (18) | 0.0320 (17) | 0.0367 (15) | 0.0001 (16) | 0.0003 (16) | −0.0017 (12) |
| N2 | 0.0335 (18) | 0.0320 (16) | 0.0368 (18) | −0.0010 (16) | −0.0010 (16) | −0.0011 (14) |
| C5 | 0.026 (2) | 0.0296 (18) | 0.0385 (19) | −0.0005 (14) | −0.0077 (17) | 0.0004 (14) |
| C12 | 0.037 (2) | 0.052 (2) | 0.042 (2) | 0.001 (3) | 0.001 (2) | −0.0009 (18) |
| C9 | 0.024 (2) | 0.0300 (19) | 0.040 (2) | −0.0022 (15) | −0.0092 (18) | 0.0041 (16) |
| C4 | 0.036 (2) | 0.038 (2) | 0.052 (2) | 0.010 (2) | −0.015 (2) | −0.0114 (18) |
| C1 | 0.039 (2) | 0.055 (3) | 0.041 (2) | 0.003 (2) | 0.0016 (19) | −0.001 (2) |
| C8 | 0.036 (2) | 0.038 (2) | 0.052 (2) | −0.0063 (19) | −0.0157 (19) | 0.0050 (19) |
| C10 | 0.046 (3) | 0.059 (3) | 0.056 (3) | −0.012 (3) | −0.002 (2) | 0.022 (2) |
| C6 | 0.060 (3) | 0.027 (2) | 0.080 (3) | 0.009 (2) | −0.029 (3) | −0.012 (2) |
| C11 | 0.042 (3) | 0.073 (3) | 0.045 (2) | −0.005 (3) | 0.006 (2) | 0.012 (2) |
| C3 | 0.046 (3) | 0.052 (3) | 0.059 (3) | 0.014 (3) | −0.013 (3) | −0.023 (2) |
| C7 | 0.058 (3) | 0.029 (2) | 0.076 (3) | −0.005 (2) | −0.024 (3) | 0.009 (2) |
| C2 | 0.043 (3) | 0.077 (4) | 0.044 (2) | 0.013 (3) | −0.005 (2) | −0.020 (2) |
| I1—Cu1 | 2.5895 (6) | C4—C6 | 1.443 (6) |
| I1—Cu1i | 2.6030 (6) | C1—C2 | 1.404 (6) |
| Cu1—N2 | 2.100 (3) | C1—H1 | 0.9300 |
| Cu1—N1 | 2.110 (3) | C8—C10 | 1.404 (6) |
| Cu1—I1ii | 2.6030 (6) | C8—C7 | 1.434 (6) |
| N1—C1 | 1.323 (5) | C10—C11 | 1.360 (7) |
| N1—C5 | 1.354 (5) | C10—H10 | 0.9300 |
| N2—C12 | 1.324 (5) | C6—C7 | 1.341 (7) |
| N2—C9 | 1.361 (5) | C6—H6 | 0.9300 |
| C5—C4 | 1.409 (5) | C11—H11 | 0.9300 |
| C5—C9 | 1.453 (5) | C3—C2 | 1.355 (7) |
| C12—C11 | 1.391 (6) | C3—H3 | 0.9300 |
| C12—H12 | 0.9300 | C7—H7 | 0.9300 |
| C9—C8 | 1.402 (5) | C2—H2 | 0.9300 |
| C4—C3 | 1.392 (7) | ||
| Cu1—I1—Cu1i | 106.715 (18) | N1—C1—C2 | 122.9 (4) |
| N2—Cu1—N1 | 79.66 (13) | N1—C1—H1 | 118.6 |
| N2—Cu1—I1 | 135.30 (10) | C2—C1—H1 | 118.6 |
| N1—Cu1—I1 | 103.90 (10) | C9—C8—C10 | 117.0 (4) |
| N2—Cu1—I1ii | 100.05 (10) | C9—C8—C7 | 119.2 (4) |
| N1—Cu1—I1ii | 134.92 (10) | C10—C8—C7 | 123.8 (4) |
| I1—Cu1—I1ii | 106.715 (18) | C11—C10—C8 | 119.8 (4) |
| C1—N1—C5 | 117.6 (3) | C11—C10—H10 | 120.1 |
| C1—N1—Cu1 | 129.6 (3) | C8—C10—H10 | 120.1 |
| C5—N1—Cu1 | 112.6 (2) | C7—C6—C4 | 122.0 (4) |
| C12—N2—C9 | 117.1 (3) | C7—C6—H6 | 119.0 |
| C12—N2—Cu1 | 129.5 (3) | C4—C6—H6 | 119.0 |
| C9—N2—Cu1 | 113.2 (3) | C10—C11—C12 | 119.0 (4) |
| N1—C5—C4 | 123.2 (3) | C10—C11—H11 | 120.5 |
| N1—C5—C9 | 117.8 (3) | C12—C11—H11 | 120.5 |
| C4—C5—C9 | 119.1 (4) | C2—C3—C4 | 119.9 (4) |
| N2—C12—C11 | 123.8 (4) | C2—C3—H3 | 120.1 |
| N2—C12—H12 | 118.1 | C4—C3—H3 | 120.1 |
| C11—C12—H12 | 118.1 | C6—C7—C8 | 120.9 (4) |
| N2—C9—C8 | 123.3 (4) | C6—C7—H7 | 119.6 |
| N2—C9—C5 | 116.6 (3) | C8—C7—H7 | 119.6 |
| C8—C9—C5 | 120.1 (4) | C3—C2—C1 | 119.4 (4) |
| C3—C4—C5 | 117.1 (4) | C3—C2—H2 | 120.3 |
| C3—C4—C6 | 124.2 (4) | C1—C2—H2 | 120.3 |
| C5—C4—C6 | 118.6 (4) |
| Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
| I1—Cu1 | 2.5895 (6) | Cu1—N2 | 2.100 (3) |
| I1—Cu1i | 2.6030 (6) | Cu1—N1 | 2.110 (3) |
| Symmetry codes: (i) x+1, y, z. |
We are grateful for financial support from the National Natural Science Foundation of China (project No. 20803070) and the Natural Science Foundation of Zhejiang Province (project No. Y4100610).
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Recently, there have been a number of reports of copper(I)-iodide complexes with 1,10-phenanthroline (phen) as a coligand. Among them, almost all complexes are disctete molecules (Healy et al., 1985; Yu et al., 2001; Yu et al., 2002; Yu et al., 2004; Zhou et al., 2005; Zhang et al., 2008) except two complexes characterized as polymeric structure (Zhang et al., 2008). We have synthesised the polymeric title complex [Cu(phen)I]n (I) (Fig.1). It is worthy of note that compound I crystallizes in a noncentrosymmetric space group of P212121, while the other copper(I)-iodide complexes with phen all crystallise in centrosymmetric space groups. The asymmmetric unit contains one Cu+ cation, one I- anion and one phen ligand. Each Cu+ cation is tetrahedrally coordinated by two iodide anion and two nitrogen atoms from a bidentate chelating phen ligand. The Cu+ cations are bridged through the iodide anions, leading to a zigzag chain structure. The Cu—I bond lengths are 2.5895 (6) and 2.6030 (6) Å, which are similar to that found in other copper(I)-iodide complexes. There are π-π interactions between adjacent phen ligands of one chain. The phen skeletons are arranged in a perfect parallel fashion with centroid-centroid distance of 3.693 (3) Å (from two adjacent C4/C5/C6/C7/C8/C9 ring and C1A/C2A/C3A/C4A/C5A/N1A ring, symmetry code A: x - 1, y, z).