Acta Cryst. (2007). E63, m1562 [ doi:10.1107/S1600536807020831 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,N')cadmate(II)]-di-![[mu]](/logos/entities/mu_rmgif.gif)
-bromido]The title compound, [CdBr2(C12H8N2)]n, is a 1:1 adduct of cadmium bromide with 1,10-phenanthroline (phen), which contains an infinite chain consisting of Cd2Br2 parallelograms sharing the Cd coners. The chain propagates along the c axis. Both the CdII atom and the phen molecule lie on a twofold rotation axis. The CdII atom is coordinated by two N atoms from a chelating phen ligand and four Br atoms to complete a distorted octahedral geometry. The closest atom-to-atom distance of 3.35 (1) Å between the phen ligands of two adjacent chains indicates the existence of ![[pi]](/logos/entities/pi_rmgif.gif)
- interactions, which result in a two-dimensional layer parallel to the bc plane. The layers are associated through weak C-H
Br hydrogen bonds.
Freshly prepared CdCO3 (0.14 g, 0.812 mmol), phen.H2O (0.10 g, 0.505 mmol), 2-bromobenzoic acid (0.10 g, 0.498 mmol), CH3OH/H2O (12 ml; v/v=1:2) were mixed and stirred for 2 h. The resulting suspension was heated in a 23 ml Teflon-lined stainless steel autoclave at 393 K for 7 d. After the autoclave was cooled to room temperature, colorless block crystals suitable for X-ray analysis were obtained.
All H atoms were positioned geometrically and treated as riding atoms, with C—H = 0.96 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./hy2057fig1thm.gif)
| Fig. 1. The structure of (I), showing the coordination geometry of Cd II atom. Displacement ellipsoids are drawn at the 40% probability level. H atoms have been omitted for clarity. [symmetry codes: (i) 1 - x, y, 1/2 - z; (ii) 1 - x, 1 - y, 1 - z; (iii) 1 - x, 1 - y, -z; (iv) x, 1 - y, z - 1/2.] |
![[Figure 2]](./hy2057fig2thm.gif)
| Fig. 2. A view of the one-dimensional chain along the c axis in (I). H atoms have been omitted for clarity. |
![[Figure 3]](./hy2057fig3thm.gif)
| Fig. 3. A packing diagram for (I), viewed down the c axis. Dashed lines indicate hydrogen bonds. |
| [CdBr2(C12H8N2)] | F(000) = 848 |
| Mr = 452.42 | Dx = 2.368 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 961 reflections |
| a = 16.7781 (7) Å | θ = 2.3–26.0° |
| b = 10.7594 (7) Å | µ = 7.99 mm−1 |
| c = 7.4213 (3) Å | T = 290 K |
| β = 108.664 (4)° | Block, colourless |
| V = 1269.26 (11) Å3 | 0.23 × 0.12 × 0.10 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1247 independent reflections |
| Radiation source: fine-focus sealed tube | 998 reflections with I > 2σ(I) |
| graphite | Rint = 0.039 |
| φ and ω scans | θmax = 26.0°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −20→18 |
| Tmin = 0.340, Tmax = 0.511 | k = −13→10 |
| 7231 measured reflections | l = −9→9 |
| 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)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.067 | w = 1/[σ2(Fo2) + 3.3613P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 1247 reflections | Δρmax = 0.59 e Å−3 |
| 79 parameters | Δρmin = −0.46 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00093 (19) |
| [CdBr2(C12H8N2)] | V = 1269.26 (11) Å3 |
| Mr = 452.42 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 16.7781 (7) Å | µ = 7.99 mm−1 |
| b = 10.7594 (7) Å | T = 290 K |
| c = 7.4213 (3) Å | 0.23 × 0.12 × 0.10 mm |
| β = 108.664 (4)° |
| Bruker SMART CCD area-detector diffractometer | 1247 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 998 reflections with I > 2σ(I) |
| Tmin = 0.340, Tmax = 0.511 | Rint = 0.039 |
| 7231 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.067 | Δρmax = 0.59 e Å−3 |
| S = 1.06 | Δρmin = −0.46 e Å−3 |
| 1247 reflections | Absolute structure: ? |
| 79 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| Cd1 | 0.5000 | 0.42497 (3) | 0.2500 | 0.04136 (18) | |
| Br1 | 0.60185 (3) | 0.58225 (4) | 0.49961 (6) | 0.04905 (19) | |
| N1 | 0.4258 (2) | 0.2472 (3) | 0.1038 (5) | 0.0462 (9) | |
| C1 | 0.3527 (3) | 0.2477 (6) | −0.0359 (8) | 0.0699 (15) | |
| H1 | 0.3291 | 0.3253 | −0.0919 | 0.084* | |
| C2 | 0.3095 (5) | 0.1378 (9) | −0.1055 (11) | 0.105 (3) | |
| H2 | 0.2563 | 0.1406 | −0.2050 | 0.125* | |
| C3 | 0.3414 (7) | 0.0289 (8) | −0.0353 (13) | 0.112 (4) | |
| H3 | 0.3095 | −0.0452 | −0.0812 | 0.135* | |
| C4 | 0.4194 (6) | 0.0225 (5) | 0.1050 (10) | 0.085 (2) | |
| C5 | 0.4646 (8) | −0.0905 (4) | 0.1855 (12) | 0.131 (7) | |
| H5 | 0.4391 | −0.1695 | 0.1417 | 0.157* | |
| C6 | 0.4603 (3) | 0.1372 (4) | 0.1760 (6) | 0.0534 (13) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cd1 | 0.0494 (3) | 0.0298 (2) | 0.0357 (3) | 0.000 | 0.00083 (19) | 0.000 |
| Br1 | 0.0535 (4) | 0.0480 (3) | 0.0414 (3) | −0.0127 (2) | 0.0092 (2) | −0.00875 (17) |
| N1 | 0.049 (2) | 0.044 (2) | 0.051 (2) | −0.0127 (17) | 0.0228 (18) | −0.0174 (16) |
| C1 | 0.053 (3) | 0.093 (4) | 0.065 (3) | −0.018 (3) | 0.021 (3) | −0.037 (3) |
| C2 | 0.074 (5) | 0.157 (7) | 0.096 (5) | −0.061 (5) | 0.044 (4) | −0.083 (5) |
| C3 | 0.150 (8) | 0.110 (6) | 0.120 (6) | −0.090 (6) | 0.103 (6) | −0.083 (6) |
| C4 | 0.149 (7) | 0.049 (3) | 0.099 (5) | −0.049 (4) | 0.098 (5) | −0.039 (3) |
| C5 | 0.29 (2) | 0.032 (3) | 0.151 (11) | −0.038 (5) | 0.178 (12) | −0.027 (3) |
| C6 | 0.082 (4) | 0.035 (2) | 0.064 (3) | −0.018 (2) | 0.052 (2) | −0.0149 (19) |
| Cd1—N1 | 2.349 (3) | C1—H1 | 0.9600 |
| Cd1—N1i | 2.349 (3) | C2—C3 | 1.323 (12) |
| Cd1—Br1 | 2.6813 (5) | C2—H2 | 0.9600 |
| Cd1—Br1i | 2.6813 (5) | C3—C4 | 1.389 (11) |
| Cd1—Br1ii | 2.9003 (5) | C3—H3 | 0.9600 |
| Cd1—Br1iii | 2.9003 (5) | C4—C6 | 1.429 (7) |
| Br1—Cd1ii | 2.9003 (5) | C4—C5 | 1.456 (11) |
| N1—C1 | 1.328 (6) | C5—C5i | 1.27 (2) |
| N1—C6 | 1.351 (6) | C5—H5 | 0.9600 |
| C1—C2 | 1.396 (8) | C6—C6i | 1.429 (10) |
| N1—Cd1—N1i | 71.03 (19) | N1—C1—C2 | 121.7 (6) |
| N1—Cd1—Br1 | 163.57 (9) | N1—C1—H1 | 119.4 |
| N1i—Cd1—Br1 | 93.92 (10) | C2—C1—H1 | 118.9 |
| N1—Cd1—Br1i | 93.92 (10) | C3—C2—C1 | 120.5 (7) |
| N1i—Cd1—Br1i | 163.57 (9) | C3—C2—H2 | 119.3 |
| Br1—Cd1—Br1i | 101.73 (2) | C1—C2—H2 | 120.2 |
| N1—Cd1—Br1ii | 86.58 (9) | C2—C3—C4 | 120.3 (6) |
| N1i—Cd1—Br1ii | 90.92 (9) | C2—C3—H3 | 119.1 |
| Br1—Cd1—Br1ii | 87.145 (15) | C4—C3—H3 | 120.6 |
| Br1i—Cd1—Br1ii | 94.797 (16) | C3—C4—C6 | 117.4 (7) |
| N1—Cd1—Br1iii | 90.92 (9) | C3—C4—C5 | 126.3 (7) |
| N1i—Cd1—Br1iii | 86.58 (9) | C6—C4—C5 | 116.4 (8) |
| Br1—Cd1—Br1iii | 94.797 (16) | C5i—C5—C4 | 123.4 (5) |
| Br1i—Cd1—Br1iii | 87.145 (15) | C5i—C5—H5 | 117.7 |
| Br1ii—Cd1—Br1iii | 176.93 (2) | C4—C5—H5 | 118.9 |
| Cd1—Br1—Cd1ii | 92.855 (15) | N1—C6—C6i | 118.7 (3) |
| C1—N1—C6 | 119.0 (4) | N1—C6—C4 | 121.1 (6) |
| C1—N1—Cd1 | 125.3 (3) | C6i—C6—C4 | 120.2 (4) |
| C6—N1—Cd1 | 115.7 (3) |
| Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···Br1iv | 0.96 | 2.88 | 3.816 (12) | 166 |
| C5—H5···Br1v | 0.96 | 2.87 | 3.815 (5) | 167 |
| Symmetry codes: (iv) x−1/2, y−1/2, z−1; (v) −x+1, y−1, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···Br1i | 0.96 | 2.88 | 3.816 (12) | 166 |
| C5—H5···Br1ii | 0.96 | 2.87 | 3.815 (5) | 167 |
| Symmetry codes: (i) x−1/2, y−1/2, z−1; (ii) −x+1, y−1, −z+1/2. |
The author gratefully acknowledges the financial support of the Education Office of Zhejiang Province (grant No. 20051316).
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Polynuclear d10 metal complexes have been found to exhibit intriguing structural and photoluminescent properties. Cl-bridged CdII polymeric complexes are of considerable interest because they may act as photoactive materials. Structures of Cl-bridged CdII polymeric complexes have been studied (Bell et al., 1982; Bigoli et al., 1983; Bonomo et al., 1989; Huang et al., 1998). However, CdII polymeric complexes with a CdBr2N2 coordination polydedron have been rarely reported. The phosphorescence and zero-field optically detected magnetic resonance studies with powder of CdX2(phen), (phen = 1,10-phenanthroline; X = Cl, Br, and I) (Kimachi et al., 1995) and the crystal structures of CdCl2(phen) and CdCl2 (2,2'-bipyridine) have been reported (Chen et al., 2003; Zhou et al., 2003). We have introduced Br- ion as a bridging ligand, and synthesized the Br-bridged Cd complex, [CdBr2(phen)]n, (I), by a hydrothermal reaction.
The structure of compound (I) (Fig. 1), contains one-dimensional chains extending in the c direction (Fig 2). Both CdII atom and phen molecule lie on the twofold rotation axis. The CdII atom is coordinated by two N atoms from a chelating phen ligand and four Br atoms to complete a distorted CdN2Br4 octahedral geometry. The average Cd—N bond length is 2.350 (3) Å and the bond lengths of Cd—Br are 2.6813 (5)Å and 2.9003 (5) Å. The Cd···Cd distance in the chain is 4.047 (1) Å, which is longer than that of the Cl-bridged Cd complex [3.931 (9) Å]. The closest atom-to-atom distance of 3.35 (1)Å between the phen ligands of two adjacent chains indicates the existence of π–π interactions, which result in a two-dimensional layer parallel to the bc plane (Fig. 3). The layers are associated through weak C—H···Br hydrogen bonds (Table 1).