Acta Cryst. (2008). E64, m1319 [ doi:10.1107/S1600536808030055 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-3-(1-methylpyrrolidin-2-yl)pyridine-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N:N']In the title polymeric complex, [HgBr2(C10H14N2)]n, each nicotine molecule is bonded to two adjacent Hg atoms, one through the pyrrolidine N atom and the other through the pyridine N atom, forming zigzag chains along [010]. The coordination around mercury is completed by two bromido ligands resulting in a distorted tetrahedral arrangement.
HgBr2 (360 mg,1 mmol) was added to a solution of 4-cyanopyridine (104 mg,1 mmol) in dmf (5 ml). The resulting mixture was stirred for about 10 min after which an white precipitate formed. S-Nicotine (3 ml) was then added dropwise to the reaction mixture and stirring was continued, during which time the precipitate changed its colour, giving a flesh colored precipitate. The precipitate was washed with ethanol and vacuum dried. Yield: 0.324 g, 62% (based on HgBr2used). The compound (100 mg) was dissolved in dmf (5 ml), the resulting solution filtered and the light-yellow filtrate transfered into a test tube and i-PrOH (10 ml) was carefully laid on the surface of the filtrate. Light-yellow block crystals were obtained after 15 days. Analysis: Found: C 23.12, H 2.82, N 5.26%; Calculated for C10H14HgBr2N2: C 22.98, H 2.70, N 5.36%.
H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 - 0.98 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C). The absolute structure parameter x (Flack, 1983) was refined to -0.006 (16) using 1083 measured Friedel pairs.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXL9 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).
![[Figure 1]](./si2110fig1thm.gif)
| Fig. 1. Molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids. All H atoms have been omitted. Symmetry transformations: A is -x + 1/2, -y, z + 1/2. |
| [HgBr2(C10H14N2)] | F(000) = 952 |
| Mr = 522.64 | Dx = 2.626 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 3183 reflections |
| a = 7.6306 (9) Å | θ = 4.5–43.1° |
| b = 11.2177 (14) Å | µ = 17.66 mm−1 |
| c = 15.443 (2) Å | T = 296 K |
| V = 1321.9 (3) Å3 | Block, light yellow |
| Z = 4 | 0.20 × 0.16 × 0.12 mm |
| Bruker SMART APEXII CCD diffractometer | 2601 independent reflections |
| Radiation source: fine-focus sealed tube | 2137 reflections with I > 2σ(I) |
| graphite | Rint = 0.057 |
| φ and ω scans | θmax = 26.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→9 |
| Tmin = 0.062, Tmax = 0.153 | k = −13→13 |
| 10476 measured reflections | l = −19→16 |
| 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)] = 0.039 | H-atom parameters constrained |
| wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0314P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max = 0.001 |
| 2601 reflections | Δρmax = 1.44 e Å−3 |
| 137 parameters | Δρmin = −1.03 e Å−3 |
| 0 restraints | Absolute structure: Flack, (1983), 1083 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: −0.006 (16) |
| [HgBr2(C10H14N2)] | V = 1321.9 (3) Å3 |
| Mr = 522.64 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 7.6306 (9) Å | µ = 17.66 mm−1 |
| b = 11.2177 (14) Å | T = 296 K |
| c = 15.443 (2) Å | 0.20 × 0.16 × 0.12 mm |
| Bruker SMART APEXII CCD diffractometer | 2601 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2137 reflections with I > 2σ(I) |
| Tmin = 0.062, Tmax = 0.153 | Rint = 0.057 |
| 10476 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
| wR(F2) = 0.076 | Δρmax = 1.44 e Å−3 |
| S = 1.00 | Δρmin = −1.03 e Å−3 |
| 2601 reflections | Absolute structure: Flack, (1983), 1083 Friedel pairs |
| 137 parameters | Flack parameter: −0.006 (16) |
| 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 | ||
| Br1 | 0.09573 (17) | 1.16819 (12) | 0.93970 (8) | 0.0688 (4) | |
| Br2 | 0.15737 (16) | 1.07721 (14) | 0.64794 (8) | 0.0622 (4) | |
| C1 | 0.2197 (13) | 0.7896 (8) | 0.7769 (6) | 0.035 (2) | |
| H1 | 0.1843 | 0.8032 | 0.7201 | 0.042* | |
| C2 | 0.3218 (11) | 0.6891 (8) | 0.7935 (6) | 0.028 (2) | |
| C3 | 0.3679 (13) | 0.6710 (9) | 0.8800 (7) | 0.044 (3) | |
| H3 | 0.4355 | 0.6053 | 0.8952 | 0.052* | |
| C4 | 0.3143 (14) | 0.7495 (9) | 0.9428 (7) | 0.045 (3) | |
| H4 | 0.3438 | 0.7373 | 1.0005 | 0.054* | |
| C5 | 0.2161 (14) | 0.8467 (9) | 0.9184 (6) | 0.040 (3) | |
| H5 | 0.1806 | 0.9003 | 0.9609 | 0.048* | |
| C6 | 0.3777 (12) | 0.6034 (8) | 0.7256 (6) | 0.034 (2) | |
| H6 | 0.4914 | 0.5703 | 0.7427 | 0.041* | |
| C7 | 0.3129 (14) | 0.4423 (10) | 0.6345 (7) | 0.055 (3) | |
| H7A | 0.2193 | 0.3962 | 0.6084 | 0.066* | |
| H7B | 0.4103 | 0.3896 | 0.6470 | 0.066* | |
| C8 | 0.3698 (16) | 0.5418 (10) | 0.5746 (7) | 0.058 (3) | |
| H8A | 0.2811 | 0.5570 | 0.5310 | 0.070* | |
| H8B | 0.4789 | 0.5216 | 0.5459 | 0.070* | |
| C9 | 0.3936 (14) | 0.6494 (9) | 0.6325 (6) | 0.047 (3) | |
| H9A | 0.3041 | 0.7086 | 0.6207 | 0.057* | |
| H9B | 0.5078 | 0.6852 | 0.6231 | 0.057* | |
| C10 | 0.2521 (15) | 0.4153 (9) | 0.7882 (7) | 0.054 (3) | |
| H10A | 0.1949 | 0.3428 | 0.7712 | 0.081* | |
| H10B | 0.1910 | 0.4499 | 0.8365 | 0.081* | |
| H10C | 0.3708 | 0.3983 | 0.8047 | 0.081* | |
| Hg1 | 0.04788 (5) | 1.06376 (4) | 0.80044 (3) | 0.04142 (13) | |
| N1 | 0.1699 (10) | 0.8672 (7) | 0.8373 (5) | 0.036 (2) | |
| N2 | 0.2514 (11) | 0.5010 (7) | 0.7140 (5) | 0.040 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0714 (10) | 0.0714 (9) | 0.0635 (8) | 0.0005 (7) | −0.0093 (6) | −0.0279 (7) |
| Br2 | 0.0525 (7) | 0.0861 (10) | 0.0481 (7) | 0.0000 (7) | 0.0091 (5) | 0.0157 (7) |
| C1 | 0.043 (6) | 0.033 (6) | 0.029 (6) | 0.005 (5) | −0.011 (4) | −0.001 (4) |
| C2 | 0.026 (5) | 0.025 (5) | 0.032 (5) | 0.002 (4) | −0.005 (4) | −0.001 (4) |
| C3 | 0.037 (6) | 0.034 (6) | 0.060 (7) | 0.000 (5) | 0.000 (5) | 0.004 (5) |
| C4 | 0.059 (8) | 0.038 (6) | 0.037 (6) | −0.015 (5) | 0.006 (5) | 0.000 (5) |
| C5 | 0.050 (7) | 0.037 (6) | 0.032 (6) | −0.011 (5) | 0.008 (5) | −0.001 (5) |
| C6 | 0.023 (5) | 0.037 (6) | 0.044 (6) | 0.005 (4) | 0.001 (4) | −0.009 (4) |
| C7 | 0.051 (7) | 0.042 (7) | 0.072 (8) | 0.012 (6) | 0.014 (6) | −0.020 (7) |
| C8 | 0.068 (8) | 0.066 (9) | 0.041 (7) | 0.010 (7) | 0.009 (6) | −0.015 (6) |
| C9 | 0.046 (7) | 0.052 (7) | 0.044 (7) | −0.011 (5) | 0.023 (5) | −0.003 (5) |
| C10 | 0.052 (7) | 0.039 (7) | 0.072 (8) | 0.007 (5) | −0.007 (6) | 0.021 (6) |
| Hg1 | 0.0416 (2) | 0.0400 (2) | 0.0427 (2) | 0.0040 (2) | −0.0016 (2) | −0.0011 (2) |
| N1 | 0.038 (5) | 0.037 (5) | 0.032 (5) | 0.002 (4) | 0.000 (4) | 0.003 (4) |
| N2 | 0.030 (4) | 0.035 (5) | 0.054 (6) | 0.006 (4) | 0.001 (4) | −0.002 (4) |
| Br1—Hg1 | 2.4760 (12) | C7—N2 | 1.470 (12) |
| Br2—Hg1 | 2.5034 (12) | C7—C8 | 1.512 (15) |
| C1—N1 | 1.332 (11) | C7—H7A | 0.9700 |
| C1—C2 | 1.394 (12) | C7—H7B | 0.9700 |
| C1—H1 | 0.9300 | C8—C9 | 1.512 (14) |
| C2—C3 | 1.396 (14) | C8—H8A | 0.9700 |
| C2—C6 | 1.485 (12) | C8—H8B | 0.9700 |
| C3—C4 | 1.372 (14) | C9—H9A | 0.9700 |
| C3—H3 | 0.9300 | C9—H9B | 0.9700 |
| C4—C5 | 1.376 (14) | C10—N2 | 1.496 (12) |
| C4—H4 | 0.9300 | C10—H10A | 0.9600 |
| C5—N1 | 1.321 (12) | C10—H10B | 0.9600 |
| C5—H5 | 0.9300 | C10—H10C | 0.9600 |
| C6—N2 | 1.510 (12) | Hg1—N2i | 2.400 (8) |
| C6—C9 | 1.532 (13) | Hg1—N1 | 2.460 (8) |
| C6—H6 | 0.9800 | N2—Hg1ii | 2.400 (8) |
| N1—C1—C2 | 124.0 (9) | C7—C8—H8B | 110.7 |
| N1—C1—H1 | 118.0 | C9—C8—H8B | 110.7 |
| C2—C1—H1 | 118.0 | H8A—C8—H8B | 108.8 |
| C1—C2—C3 | 115.8 (9) | C8—C9—C6 | 106.0 (8) |
| C1—C2—C6 | 123.6 (9) | C8—C9—H9A | 110.5 |
| C3—C2—C6 | 120.6 (8) | C6—C9—H9A | 110.5 |
| C4—C3—C2 | 120.5 (10) | C8—C9—H9B | 110.5 |
| C4—C3—H3 | 119.7 | C6—C9—H9B | 110.5 |
| C2—C3—H3 | 119.7 | H9A—C9—H9B | 108.7 |
| C3—C4—C5 | 118.5 (10) | N2—C10—H10A | 109.5 |
| C3—C4—H4 | 120.7 | N2—C10—H10B | 109.5 |
| C5—C4—H4 | 120.7 | H10A—C10—H10B | 109.5 |
| N1—C5—C4 | 122.9 (10) | N2—C10—H10C | 109.5 |
| N1—C5—H5 | 118.6 | H10A—C10—H10C | 109.5 |
| C4—C5—H5 | 118.6 | H10B—C10—H10C | 109.5 |
| C2—C6—N2 | 113.1 (8) | N2i—Hg1—N1 | 96.8 (3) |
| C2—C6—C9 | 117.9 (8) | N2i—Hg1—Br1 | 111.1 (2) |
| N2—C6—C9 | 101.3 (7) | N1—Hg1—Br1 | 99.6 (2) |
| C2—C6—H6 | 108.0 | N2i—Hg1—Br2 | 104.3 (2) |
| N2—C6—H6 | 108.0 | N1—Hg1—Br2 | 98.36 (19) |
| C9—C6—H6 | 108.0 | Br1—Hg1—Br2 | 137.68 (5) |
| N2—C7—C8 | 105.8 (8) | C5—N1—C1 | 118.3 (8) |
| N2—C7—H7A | 110.6 | C5—N1—Hg1 | 118.5 (7) |
| C8—C7—H7A | 110.6 | C1—N1—Hg1 | 122.2 (6) |
| N2—C7—H7B | 110.6 | C7—N2—C10 | 110.6 (8) |
| C8—C7—H7B | 110.6 | C7—N2—C6 | 103.7 (8) |
| H7A—C7—H7B | 108.7 | C10—N2—C6 | 113.3 (8) |
| C7—C8—C9 | 105.2 (8) | C7—N2—Hg1ii | 110.9 (6) |
| C7—C8—H8A | 110.7 | C10—N2—Hg1ii | 105.2 (6) |
| C9—C8—H8A | 110.7 | C6—N2—Hg1ii | 113.3 (6) |
| Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x, y−1/2, −z+3/2. |
This work was financially supported by the Natural Science Foundation of Jiangsu Province Education office (No. 04KJB150015). We also thank Dr Zaichao Zhang for his support.
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Haendler, H. M. (1990). Acta Cryst. C46, 2054–2057.
Meyer, G., Berners, A. & Pantenburg, I. (2006). Z. Anorg. Allg. Chem. 632, 34–35.
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Udupa, M. R. & Krebs, B. (1980). Inorg. Chim. Acta, 40, 161–164.
Compounds containing nicotine [3-(1-methyl-2-pyrrolidinyl) pyridine] have been reported to form molecular and polynuclear complexes (Meyer et al., 2006; Haendler, 1990). The crystal structure of the title compound appeared to be isostructural with the dichlorido(nicotine)mercury(II) chain polymer complex (Udupa & Krebs, 1980).
As illustrated in Fig. 1, each nicotine molecule in (I) is coordinated to two adjacent mercury atoms, one through the pyrrolidine nitrogen (Hg—N 2.400 (8) Å) and the other through the pyridine nitrogen (Hg—N 2.460 (8) Å), forming zigzag polymeric chains along the b axis. The coordination around mercury is completed by two bromine ligands (Hg—Br 2.4760 (12) and 2.5034 (12) Å), resulting in a distorted tetrahedral arrangement. In addition, the absolut configurations of C6 and N2 can be given as S (S-nicotine was used as a starting material). No notable interactions were found between polymeric chains.