PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1026.
Published online 2008 July 12. doi:  10.1107/S1600536808020904
PMCID: PMC2961948

catena-Poly[[diiodidomercury(II)]-μ-nicotine-κ2 N:N′]

Abstract

The title polymeric complex, [HgI2(C10H14N2)]n, was prepared from a solution of nicotine, mercury(II) iodide and 4-cyano­pyridine in dimethyl­formamide. Each nicotine mol­ecule is bonded to two Hg atoms, one through the pyrrolidine N atom and the other through the pyridine N atom, forming infinite zigzag polymeric chains. The coordin­ation around mercury is completed by two iodide ligands, resulting in a distorted tetra­hedral arrangement.

Related literature

For related literature, see: Udupa & Krebs, (1980 [triangle]); Meyer et al., (2006 [triangle]); Haendler, (1990 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1026-scheme1.jpg

Experimental

Crystal data

  • [HgI2(C10H14N2)]
  • M r = 616.62
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1026-efi3.jpg
  • a = 7.7171 (2) Å
  • b = 11.1548 (3) Å
  • c = 15.9646 (4) Å
  • V = 1374.28 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 15.67 mm−1
  • T = 123 (2) K
  • 0.20 × 0.16 × 0.12 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.062, T max = 0.15
  • 6248 measured reflections
  • 2344 independent reflections
  • 2274 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.049
  • S = 0.92
  • 2344 reflections
  • 137 parameters
  • 6 restraints
  • H-atom parameters constrained
  • Δρmax = 0.89 e Å−3
  • Δρmin = −1.31 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 852 Friedel pairs
  • Flack parameter: 0.033 (5)

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 [triangle]).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020904/hg2420sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020904/hg2420Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (No. 50572039) and the Natural Science Foundation of Jiangsu Province (BK2006199).

supplementary crystallographic information

Comment

Numerous complexes of nicotine [3-(1-methyl-2-pyrrolidinyl)pyridine] have been reported to form molecular complexes and polycomplexes with metals (Udupa & Krebs, 1980; Meyer et al., 2006; Haendler, 1990). However, the crystal structure of the polycomplex, di-iodido(nicotine)mercury(II), has not been reported so far. In order to further explore the structural chemistry of nicotine complexes, we synthesized and determined the structure of the title compound (I).

As illustrated in Fig. 1, each nicotine molecule in (I) is coordinated to two adjacent mercury atoms, one through the pyrrolidine nitrogen (Hg—N 2.428 (7) Å) and the other through the pyridine nitrogen (Hg—N 2.454 (5) Å), forming zigzag polymeric chains. The coordination around mercury is completed by two iodide ligands (Hg—I 2.6819 (6) and 2.6536 (5) Å), resulting in a distorted tetrahedral arrangement. In addition, the absolute 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.

Examples of closely related compounds containing nicotine ligands include a mercury(II) chain polymer (Udupa & Krebs, 1980), a helical silver(I) coordination polymer (Meyer et al., 2006) and a chloride-nicotine copper(II) complex (Haendler, 1990).

Experimental

HgI2 (454 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: 0.435 g, 70% (based on HgI2used). 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 34.52, H 3.90, N 7.90%; Calculated for C10H14HgI2N2: C 34.35, H 4.04, N 8.01%.

Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95–1.00 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Figures

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.

Crystal data

[HgI2(C10H14N2)]F000 = 1096
Mr = 616.62Dx = 2.980 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2274 reflections
a = 7.7171 (2) Åθ = 2.1–26.4º
b = 11.1548 (3) ŵ = 15.67 mm1
c = 15.9646 (4) ÅT = 123 (2) K
V = 1374.28 (6) Å3Block, light-yellow
Z = 40.20 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer2344 independent reflections
Radiation source: fine-focus sealed tube2274 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 123(2) Kθmax = 25.5º
[var phi] and ω scansθmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2000)h = −9→6
Tmin = 0.062, Tmax = 0.15k = −13→11
6248 measured reflectionsl = −19→15

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.023  w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.049(Δ/σ)max = 0.002
S = 0.92Δρmax = 0.89 e Å3
2344 reflectionsΔρmin = −1.31 e Å3
137 parametersExtinction correction: none
6 restraintsAbsolute structure: Flack (1983), 852 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.033 (5)
Secondary atom site location: difference Fourier map

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.7832 (10)0.7760 (5)0.7209 (4)0.0132 (17)
H10.81930.78990.77700.016*
C20.6807 (9)0.6765 (5)0.7059 (5)0.0103 (16)
C30.6386 (10)0.6555 (6)0.6213 (5)0.0140 (17)
H30.57180.58740.60600.017*
C40.6952 (10)0.7348 (6)0.5605 (5)0.0179 (18)
H40.66610.72190.50340.022*
C50.7939 (10)0.8325 (6)0.5829 (5)0.0136 (17)
H50.83330.88580.54060.016*
C60.6217 (10)0.5906 (6)0.7722 (4)0.0119 (17)
H60.50720.55720.75430.014*
C70.6751 (11)0.4290 (6)0.8612 (5)0.0188 (19)
H7A0.76620.37990.88820.023*
H7B0.57560.37660.84740.023*
C80.6183 (11)0.5305 (6)0.9193 (4)0.0185 (19)
H8A0.70630.54530.96330.022*
H8B0.50630.51150.94650.022*
C90.6006 (10)0.6397 (6)0.8611 (4)0.0140 (17)
H9A0.48570.67780.86810.017*
H9B0.69150.69980.87350.017*
C100.7411 (11)0.4025 (6)0.7151 (5)0.023 (2)
H10A0.79710.32770.73240.034*
H10B0.80380.43680.66740.034*
H10C0.62100.38610.69880.034*
Hg10.95797 (4)1.05075 (2)0.698176 (18)0.01298 (8)
I10.84450 (6)1.06434 (4)0.85667 (3)0.01766 (13)
I20.91255 (7)1.16336 (4)0.55341 (3)0.02021 (14)
N10.8355 (8)0.8542 (4)0.6627 (4)0.0104 (14)
N20.7431 (9)0.4874 (4)0.7847 (3)0.0126 (15)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.016 (4)0.017 (3)0.007 (4)−0.001 (3)−0.002 (3)0.008 (3)
C20.010 (2)0.011 (2)0.010 (2)0.0016 (17)0.0016 (17)−0.0009 (17)
C30.011 (4)0.016 (3)0.016 (5)0.001 (3)−0.005 (3)−0.001 (3)
C40.019 (5)0.022 (4)0.012 (5)0.005 (4)−0.007 (4)0.000 (4)
C50.014 (4)0.022 (4)0.005 (4)0.007 (4)−0.001 (3)0.002 (3)
C60.010 (4)0.014 (3)0.012 (4)0.001 (3)−0.001 (3)0.002 (3)
C70.028 (5)0.018 (4)0.011 (4)0.001 (4)0.008 (4)0.003 (3)
C80.024 (5)0.021 (4)0.011 (4)−0.003 (4)0.006 (4)−0.001 (3)
C90.020 (4)0.016 (3)0.007 (4)0.004 (3)0.005 (3)−0.001 (3)
C100.023 (5)0.017 (4)0.029 (6)−0.001 (4)0.002 (4)−0.006 (4)
Hg10.01563 (16)0.01506 (14)0.00825 (16)−0.00253 (13)−0.00074 (12)0.00158 (13)
I10.0168 (3)0.0258 (3)0.0105 (3)−0.0004 (2)0.0026 (2)−0.0031 (2)
I20.0254 (3)0.0222 (3)0.0131 (3)−0.0003 (2)−0.0033 (2)0.0079 (2)
N10.015 (3)0.010 (3)0.006 (3)−0.003 (3)0.002 (3)0.002 (3)
N20.021 (4)0.007 (3)0.009 (4)−0.005 (3)0.002 (3)0.003 (3)

Geometric parameters (Å, °)

C1—N11.336 (8)C7—H7A0.9900
C1—C21.384 (9)C7—H7B0.9900
C1—H10.9500C8—C91.538 (9)
C2—C31.409 (9)C8—H8A0.9900
C2—C61.499 (9)C8—H8B0.9900
C3—C41.384 (9)C9—H9A0.9900
C3—H30.9500C9—H9B0.9900
C4—C51.376 (9)C10—N21.460 (8)
C4—H40.9500C10—H10A0.9800
C5—N11.336 (9)C10—H10B0.9800
C5—H50.9500C10—H10C0.9800
C6—N21.498 (8)Hg1—N2i2.428 (7)
C6—C91.530 (9)Hg1—N12.454 (5)
C6—H61.0000Hg1—I22.6536 (5)
C7—N21.481 (9)Hg1—I12.6819 (6)
C7—C81.528 (9)N2—Hg1ii2.428 (7)
N1—C1—C2125.1 (7)C7—C8—H8B110.9
N1—C1—H1117.4C9—C8—H8B110.9
C2—C1—H1117.4H8A—C8—H8B108.9
C1—C2—C3115.5 (6)C6—C9—C8105.5 (5)
C1—C2—C6124.3 (7)C6—C9—H9A110.6
C3—C2—C6120.1 (6)C8—C9—H9A110.6
C4—C3—C2119.5 (6)C6—C9—H9B110.6
C4—C3—H3120.2C8—C9—H9B110.6
C2—C3—H3120.2H9A—C9—H9B108.8
C5—C4—C3119.9 (7)N2—C10—H10A109.5
C5—C4—H4120.0N2—C10—H10B109.5
C3—C4—H4120.0H10A—C10—H10B109.5
N1—C5—C4121.6 (7)N2—C10—H10C109.5
N1—C5—H5119.2H10A—C10—H10C109.5
C4—C5—H5119.2H10B—C10—H10C109.5
N2—C6—C2113.2 (6)N2i—Hg1—N197.59 (19)
N2—C6—C9102.6 (5)N2i—Hg1—I2111.18 (13)
C2—C6—C9117.3 (6)N1—Hg1—I299.85 (13)
N2—C6—H6107.7N2i—Hg1—I1102.73 (13)
C2—C6—H6107.7N1—Hg1—I198.19 (13)
C9—C6—H6107.7I2—Hg1—I1138.749 (19)
N2—C7—C8106.1 (5)C1—N1—C5118.2 (6)
N2—C7—H7A110.5C1—N1—Hg1122.6 (4)
C8—C7—H7A110.5C5—N1—Hg1118.3 (4)
N2—C7—H7B110.5C10—N2—C7109.8 (5)
C8—C7—H7B110.5C10—N2—C6113.0 (6)
H7A—C7—H7B108.7C7—N2—C6103.1 (5)
C7—C8—C9104.2 (6)C10—N2—Hg1ii106.5 (5)
C7—C8—H8A110.9C7—N2—Hg1ii111.8 (5)
C9—C8—H8A110.9C6—N2—Hg1ii112.7 (4)

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2420).

References

  • Bruker (2000). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin,USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Haendler, H. M. (1990). Acta Cryst. C46, 2054–2057.
  • Meyer, G., Berners, A. & Pantenburg, I. (2006). Z. Anorg. Allg. Chem.632, 34–35.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Udupa, M. R. & Krebs, B. (1980). Inorg. Chim. Acta, 40, 161–164.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography