Acta Cryst. (2007). E63, m1746 [ doi:10.1107/S1600536807023318 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-chlorido]]The asymmetric unit of the title compound, {(C12H10N2)[BiCl4]}n, comprises one 1,10-phenanthrolinium dication and one Bi atom with two terminal and two bridging chloride anions. The Bi atoms adopt a distorted octahedral configuration and are each bridged to two other Bi atoms by four chloride ligands to generate a one-dimensional polymer chain running along a. C-H
Cl hydrogen bonds link the phenanthrolinium dications to these chlorobismuthate chains.
Bismuth trichloride (0.5 mmol) was dissolved in 20 ml of dicholoromethane, and 0.5 mmol of 1,10-phenanthroline were added under stirring at room temperature. Pale yellow crystals precipitated after a few days and were filtered, washed with acetone and dried under vacuum. Yield 81%. m.p.: 421 K. Analysis calculated for C12H10BiCl4N2 : C 27.04, H 1.89, N 5.26%. Found: C 27.32, H 1.73, N 5.45%.
All H atoms were placed geometrically (C—H = 0.93 Å, N—H = 0.88 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier). Atoms N1, N2, C4, C7, C11 and C12 of the 1,10-phenanthrolinium cations are disordered over two positions with occupancies that were fixed at at 0.58 (1) and 0.42 (1) for all five atoms in the final stages of the refinement. Atoms C1—C3, C5, C7 and C8—C10 were common to both disorder components, while the atom pairs C4, N1'; C7 N2'; N1, C4' and N2, C7' shared identical coordinates.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./at2292fig1thm.gif)
| Fig. 1. The structure of (I) with 30% probability displacement ellipsoids and the atom-numbering scheme. Unlabeled atoms are related to the corresponding labeled atoms by the symmetry code -x + 1,-y + 1,-z + 1 with Cl2 related to Cl2A by the symmetry code -x + 2,-y + 1,-z + 1. |
![[Figure 2]](./at2292fig2thm.gif)
| Fig. 2. The crystal packing of (I) viewed down the c axis. Polymeric chains of chloride bridged octachlorodibismuthate tetraanions are linked to the cations by intermolecular C—H···Cl hydrogen bonds drawn as dashed lines. |
![[Figure 3]](./at2292fig3thm.gif)
| Fig. 3. A representation of the disorder in the phenathrolinium cations of (I). Atoms of the minor component are linked by double dashed lines and atoms sharing common coordinates are displayed as filled spheres. |
| (C12H10N2)[BiCl4] | Z = 2 |
| Mr = 533.00 | F(000) = 494 |
| Triclinic, P1 | Dx = 2.200 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.2569 (14) Å | Cell parameters from 2619 reflections |
| b = 10.1924 (19) Å | θ = 2.2–26.6° |
| c = 12.139 (2) Å | µ = 11.61 mm−1 |
| α = 77.944 (3)° | T = 298 K |
| β = 75.044 (2)° | Block, yellow |
| γ = 69.313 (2)° | 0.22 × 0.21 × 0.20 mm |
| V = 804.6 (3) Å3 |
| CCD area detector diffractometer | 2804 independent reflections |
| Radiation source: fine-focus sealed tube | 2469 reflections with I > 2σ(I) |
| graphite | Rint = 0.019 |
| φ and ω scans | θmax = 25.0°, θmin = 1.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.088, Tmax = 0.098 | k = −11→12 |
| 4232 measured reflections | l = −14→13 |
| 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.105 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.0769P)2 + 0.0334P] where P = (Fo2 + 2Fc2)/3 |
| 2804 reflections | (Δ/σ)max < 0.001 |
| 192 parameters | Δρmax = 3.70 e Å−3 |
| 13 restraints | Δρmin = −1.53 e Å−3 |
| (C12H10N2)[BiCl4] | γ = 69.313 (2)° |
| Mr = 533.00 | V = 804.6 (3) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.2569 (14) Å | Mo Kα radiation |
| b = 10.1924 (19) Å | µ = 11.61 mm−1 |
| c = 12.139 (2) Å | T = 298 K |
| α = 77.944 (3)° | 0.22 × 0.21 × 0.20 mm |
| β = 75.044 (2)° |
| CCD area detector diffractometer | 2804 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2469 reflections with I > 2σ(I) |
| Tmin = 0.088, Tmax = 0.098 | Rint = 0.019 |
| 4232 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.105 | Δρmax = 3.70 e Å−3 |
| S = 1.00 | Δρmin = −1.53 e Å−3 |
| 2804 reflections | Absolute structure: ? |
| 192 parameters | Flack parameter: ? |
| 13 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 | Occ. (<1) | |
| Bi1 | 0.68159 (4) | 0.57991 (3) | 0.56389 (2) | 0.03303 (15) | |
| Cl1 | 0.3605 (3) | 0.6925 (2) | 0.4619 (2) | 0.0430 (5) | |
| Cl2 | 1.0241 (4) | 0.4526 (3) | 0.6542 (2) | 0.0473 (5) | |
| Cl3 | 0.6950 (4) | 0.8238 (3) | 0.5580 (2) | 0.0544 (6) | |
| Cl4 | 0.4662 (4) | 0.5734 (3) | 0.7672 (2) | 0.0570 (7) | |
| N1 | 0.3086 (11) | −0.0610 (8) | −0.0603 (7) | 0.041 (2) | 0.580 (11) |
| H1A | 0.2899 | −0.1385 | −0.0233 | 0.049* | 0.580 (11) |
| N2 | 0.1154 (12) | −0.0722 (9) | 0.1714 (7) | 0.0421 (19) | 0.580 (11) |
| H2A | 0.1572 | −0.1471 | 0.1381 | 0.050* | 0.580 (11) |
| C4 | 0.2683 (12) | 0.1853 (9) | −0.0634 (7) | 0.0399 (18) | 0.580 (11) |
| C7 | 0.0775 (12) | 0.1708 (9) | 0.1679 (7) | 0.0407 (19) | 0.580 (11) |
| C4' | 0.3086 (11) | −0.0610 (8) | −0.0603 (7) | 0.041 (2) | 0.420 (11) |
| C7' | 0.1154 (12) | −0.0722 (9) | 0.1714 (7) | 0.0421 (19) | 0.420 (11) |
| N1' | 0.2683 (12) | 0.1853 (9) | −0.0634 (7) | 0.0399 (18) | 0.420 (11) |
| H1' | 0.2268 | 0.2581 | −0.0276 | 0.048* | 0.420 (11) |
| N2' | 0.0775 (12) | 0.1708 (9) | 0.1679 (7) | 0.0407 (19) | 0.420 (11) |
| H2' | 0.0972 | 0.2486 | 0.1325 | 0.049* | 0.420 (11) |
| C1 | 0.4030 (14) | −0.0518 (10) | −0.1717 (8) | 0.044 (2) | |
| H1 | 0.4517 | −0.1329 | −0.2078 | 0.053* | |
| C2 | 0.4303 (16) | 0.0681 (11) | −0.2330 (9) | 0.052 (3) | |
| H2 | 0.4927 | 0.0715 | −0.3103 | 0.063* | |
| C3 | 0.3575 (16) | 0.1941 (13) | −0.1730 (10) | 0.060 (3) | |
| H3 | 0.3743 | 0.2792 | −0.2120 | 0.072* | |
| C5 | 0.2425 (12) | 0.0623 (9) | −0.0078 (7) | 0.0339 (18) | |
| C6 | 0.1431 (13) | 0.0550 (9) | 0.1109 (8) | 0.0363 (19) | |
| C8 | −0.0172 (15) | 0.1638 (12) | 0.2782 (9) | 0.054 (3) | |
| H8 | −0.0625 | 0.2437 | 0.3156 | 0.065* | |
| C9 | −0.0488 (18) | 0.0387 (13) | 0.3378 (10) | 0.060 (3) | |
| H9 | −0.1176 | 0.0348 | 0.4139 | 0.072* | |
| C10 | 0.0207 (14) | −0.0742 (11) | 0.2841 (9) | 0.049 (2) | |
| H10 | 0.0045 | −0.1588 | 0.3249 | 0.059* | |
| C11 | 0.203 (3) | 0.311 (2) | −0.0032 (15) | 0.051 (4) | 0.580 (11) |
| H11 | 0.2299 | 0.3932 | −0.0413 | 0.061* | 0.580 (11) |
| C12 | 0.107 (2) | 0.3055 (17) | 0.1029 (14) | 0.044 (4) | 0.580 (11) |
| H12 | 0.0569 | 0.3867 | 0.1389 | 0.053* | 0.580 (11) |
| C11' | 0.278 (3) | −0.195 (2) | 0.011 (2) | 0.043 (6) | 0.420 (11) |
| H11' | 0.3238 | −0.2774 | −0.0236 | 0.051* | 0.420 (11) |
| C12' | 0.189 (3) | −0.1999 (19) | 0.1209 (18) | 0.040 (5) | 0.420 (11) |
| H12' | 0.1748 | −0.2839 | 0.1639 | 0.047* | 0.420 (11) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Bi1 | 0.0318 (2) | 0.0319 (2) | 0.0345 (2) | −0.00910 (14) | −0.00571 (13) | −0.00526 (13) |
| Cl1 | 0.0442 (12) | 0.0359 (11) | 0.0463 (13) | −0.0084 (9) | −0.0142 (10) | −0.0009 (9) |
| Cl2 | 0.0451 (13) | 0.0528 (14) | 0.0400 (12) | −0.0084 (10) | −0.0132 (10) | −0.0042 (10) |
| Cl3 | 0.0726 (17) | 0.0413 (13) | 0.0529 (14) | −0.0248 (12) | −0.0050 (12) | −0.0112 (10) |
| Cl4 | 0.0592 (16) | 0.0574 (15) | 0.0435 (14) | −0.0164 (12) | 0.0023 (11) | −0.0027 (11) |
| N1 | 0.043 (5) | 0.044 (5) | 0.040 (5) | −0.014 (4) | −0.013 (4) | −0.007 (4) |
| N2 | 0.035 (4) | 0.043 (5) | 0.049 (5) | −0.010 (4) | −0.015 (4) | −0.003 (4) |
| C4 | 0.041 (4) | 0.040 (5) | 0.036 (4) | −0.009 (4) | −0.009 (4) | −0.004 (3) |
| C7 | 0.038 (4) | 0.042 (5) | 0.039 (5) | −0.008 (4) | −0.009 (4) | −0.007 (4) |
| C4' | 0.043 (5) | 0.044 (5) | 0.040 (5) | −0.014 (4) | −0.013 (4) | −0.007 (4) |
| C7' | 0.035 (4) | 0.043 (5) | 0.049 (5) | −0.010 (4) | −0.015 (4) | −0.003 (4) |
| N1' | 0.041 (4) | 0.040 (5) | 0.036 (4) | −0.009 (4) | −0.009 (4) | −0.004 (3) |
| N2' | 0.038 (4) | 0.042 (5) | 0.039 (5) | −0.008 (4) | −0.009 (4) | −0.007 (4) |
| C1 | 0.046 (5) | 0.045 (5) | 0.046 (6) | −0.017 (4) | −0.010 (4) | −0.010 (4) |
| C2 | 0.049 (6) | 0.060 (7) | 0.046 (6) | −0.012 (5) | −0.003 (5) | −0.018 (5) |
| C3 | 0.055 (6) | 0.067 (7) | 0.056 (7) | −0.010 (5) | −0.022 (5) | −0.007 (5) |
| C5 | 0.028 (4) | 0.036 (5) | 0.038 (5) | −0.006 (3) | −0.010 (4) | −0.006 (4) |
| C6 | 0.041 (5) | 0.036 (5) | 0.037 (5) | −0.015 (4) | −0.014 (4) | 0.000 (4) |
| C8 | 0.043 (5) | 0.062 (7) | 0.058 (7) | −0.011 (5) | −0.008 (5) | −0.026 (5) |
| C9 | 0.064 (7) | 0.073 (8) | 0.043 (6) | −0.025 (6) | −0.016 (5) | 0.001 (5) |
| C10 | 0.038 (5) | 0.047 (6) | 0.053 (6) | −0.016 (4) | −0.008 (4) | 0.017 (5) |
| C11 | 0.044 (9) | 0.055 (11) | 0.051 (10) | −0.021 (8) | 0.003 (8) | −0.009 (8) |
| C12 | 0.043 (7) | 0.042 (7) | 0.045 (7) | −0.011 (6) | −0.009 (6) | −0.005 (6) |
| C11' | 0.038 (12) | 0.031 (11) | 0.059 (14) | −0.018 (9) | 0.000 (10) | −0.003 (10) |
| C12' | 0.039 (8) | 0.045 (9) | 0.036 (8) | −0.015 (7) | −0.010 (7) | −0.003 (7) |
| Bi1—Cl3 | 2.508 (2) | C7—C12 | 1.492 (18) |
| Bi1—Cl4 | 2.560 (2) | C1—C2 | 1.343 (14) |
| Bi1—Cl1 | 2.699 (2) | C1—H1 | 0.9300 |
| Bi1—Cl2 | 2.756 (2) | C2—C3 | 1.474 (15) |
| Bi1—Cl2i | 2.937 (2) | C2—H2 | 0.9300 |
| Bi1—Cl1ii | 2.985 (2) | C3—H3 | 0.9300 |
| Cl1—Bi1ii | 2.985 (2) | C5—C6 | 1.435 (13) |
| Cl2—Bi1i | 2.937 (2) | C8—C9 | 1.393 (16) |
| N1—C1 | 1.349 (12) | C8—H8 | 0.9300 |
| N1—C5 | 1.403 (11) | C9—C10 | 1.317 (16) |
| N1—H1A | 0.8600 | C9—H9 | 0.9300 |
| N2—C10 | 1.363 (13) | C10—H10 | 0.9300 |
| N2—C6 | 1.405 (12) | C11—C12 | 1.30 (2) |
| N2—H2A | 0.8600 | C11—H11 | 0.9300 |
| C4—C3 | 1.321 (14) | C12—H12 | 0.9300 |
| C4—C5 | 1.345 (12) | C11'—C12' | 1.32 (3) |
| C4—C11 | 1.475 (19) | C11'—H11' | 0.9300 |
| C7—C8 | 1.338 (13) | C12'—H12' | 0.9300 |
| C7—C6 | 1.367 (12) | ||
| Cl3—Bi1—Cl4 | 94.42 (9) | N1—C1—H1 | 118.3 |
| Cl3—Bi1—Cl1 | 89.50 (9) | C1—C2—C3 | 117.3 (10) |
| Cl4—Bi1—Cl1 | 93.70 (8) | C1—C2—H2 | 121.3 |
| Cl3—Bi1—Cl2 | 92.93 (9) | C3—C2—H2 | 121.3 |
| Cl4—Bi1—Cl2 | 89.82 (9) | C4—C3—C2 | 119.6 (11) |
| Cl1—Bi1—Cl2 | 175.56 (6) | C4—C3—H3 | 120.2 |
| Cl3—Bi1—Cl2i | 90.29 (8) | C2—C3—H3 | 120.2 |
| Cl4—Bi1—Cl2i | 170.84 (8) | C4—C5—N1 | 123.1 (8) |
| Cl1—Bi1—Cl2i | 94.19 (7) | C4—C5—C6 | 119.2 (7) |
| Cl2—Bi1—Cl2i | 82.09 (7) | N1—C5—C6 | 117.7 (8) |
| Cl3—Bi1—Cl1ii | 171.16 (8) | C7—C6—N2 | 118.8 (8) |
| Cl4—Bi1—Cl1ii | 90.50 (8) | C7—C6—C5 | 120.7 (8) |
| Cl1—Bi1—Cl1ii | 82.85 (7) | N2—C6—C5 | 120.5 (8) |
| Cl2—Bi1—Cl1ii | 94.43 (7) | C7—C8—C9 | 120.9 (10) |
| Cl2i—Bi1—Cl1ii | 85.88 (7) | C7—C8—H8 | 119.6 |
| Bi1—Cl1—Bi1ii | 97.15 (7) | C9—C8—H8 | 119.6 |
| Bi1—Cl2—Bi1i | 97.91 (7) | C10—C9—C8 | 118.6 (10) |
| C1—N1—C5 | 116.6 (8) | C10—C9—H9 | 120.7 |
| C1—N1—H1A | 121.7 | C8—C9—H9 | 120.7 |
| C5—N1—H1A | 121.7 | C9—C10—N2 | 122.7 (9) |
| C10—N2—C6 | 118.4 (8) | C9—C10—H10 | 118.6 |
| C10—N2—H2A | 120.8 | N2—C10—H10 | 118.6 |
| C6—N2—H2A | 120.8 | C12—C11—C4 | 119.6 (15) |
| C3—C4—C5 | 119.9 (9) | C12—C11—H11 | 120.2 |
| C3—C4—C11 | 119.0 (10) | C4—C11—H11 | 120.2 |
| C5—C4—C11 | 121.1 (10) | C11—C12—C7 | 120.8 (15) |
| C8—C7—C6 | 120.5 (9) | C11—C12—H12 | 119.6 |
| C8—C7—C12 | 121.1 (10) | C7—C12—H12 | 119.6 |
| C6—C7—C12 | 118.4 (9) | C12'—C11'—H11' | 118.9 |
| C2—C1—N1 | 123.5 (9) | C11'—C12'—H12' | 121.0 |
| C2—C1—H1 | 118.3 |
| Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C12—H12···Cl2ii | 0.93 | 3.10 | 3.951 (17) | 153 |
| C12'—H12'···Cl2iii | 0.93 | 2.90 | 3.77 (2) | 155 |
| Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C12—H12···Cl2i | 0.93 | 3.10 | 3.951 (17) | 153 |
| C12'—H12'···Cl2ii | 0.93 | 2.90 | 3.77 (2) | 155 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
We acknowledge the financial support of the Shandong Province Science Foundation, and the State Key Laboratory of Crystal Materials, Shandong University, People's Republic of China.
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The coordination chemistry of bismuth(III) is not widely investigated, although a number of adducts formed by nitrogen-containing ligands with bismuth(III) salts have been reported (Summers et al., 1994). More recently however, bismuth(III) coordination chemistry has gained more prominence, particularly in the light of the role of bismuth compounds in 212Bi isotope therapy in cancer research (Sun et al., 1997) and the use of bismuth complexes in the treatment of peptic ulcers (Sun et al., 1997; Baxter, 1992). In a continuation of our studies of metal complexes with nitrogen ligands and salts of protonated nitrogen ligands with metal containing anions, we report here the synthesis and structure of the title compound, (phenH22+)2(Bi2Cl84-).
The asymmetric unit of the title compound, C12H10BiCl4N2, comprises one 1,10-phenanthrolinium dication and one half of an octachlorodibismuthate tetraanion which lies about an inversion centre and forms the tetranion via Bi1—Cl1—Bi1i and Bi1—Cl1i—Bi1i bridges [i = - x + 1, - y + 1, - z + 1] to build the complex (phenH22+)2(Bi2Cl84-). A view of the formula unit made up of two cations and anion is shown in Fig. 1. The dications are disordered with the two disorder components related in a head to tail fashion Fig 3.
The dimeric [Bi2Cl8]4- tetraanions are made up from two octahedra sharing a common edge. The coordination geometry about Bi is distorted octahedral with Cl—Bi—Cl angles varying from 82.85 (7) - 94.43 (7)° for cis and 71.16 (8) -175.56 (6)° for trans arrangements. The Bi—Cl bond distances also vary with the role they play in the structure. The terminal Bi—Cl3 [2.508 (2) Å] and Bi—Cl4 [2.560 (2) Å] bonds are significantly shorter than those involving Cl bridges which range from 2.699 (2) to 2.985 (2) Å.
In the crystal tetraanions are further linked by Bi1—Cl2ii—Bi1 bridges [ii = - x + 2, - y + 1, - z + 1] to generate a one-dimensional polymer chain running along c axis. Cations and anions are linked by C—H···Cl hydrogen bonds (Fig. 2).