catena-Poly[[diiodidomercury(II)]-μ-nicotine-κ2N:N′]

Jiang, Z.; Tang, G.; Lu, L.

doi:10.1107/S1600536808020904

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1026

doi:10.1107/S1600536808020904

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catena-Poly[[diiodidomercury(II)]-μ-nicotine-κ²N:N′]

Zhengjing Jiang,^a,^b Guodong Tang ^a,^b and Lude Lu ^a ^*

^aKey Laboratory for Soft Chemistry and Functional Materials of the Ministry of Education, Nanjing University of Science and Technology, 200 Xiaolingwei, Nanjing 210094, Jiangsu, People's Republic of China, and ^bDepartment of Chemistry, Huaiyin Teachers College, Huai'an 223300, Jiangsu, People's Republic of China
^*Correspondence e-mail: lulude17@yahoo.com.cn

(Received 28 June 2008; accepted 7 July 2008; online 12 July 2008)

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 ); Meyer et al., (2006 ); Haendler, (1990 ).

Experimental

Crystal data

[HgI₂(C₁₀H₁₄N₂)]
M_r = 616.62
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.023
wR(F²) = 0.049
S = 0.92
2344 reflections
137 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −1.31 e Å⁻³
Absolute structure: Flack (1983 ), 852 Friedel pairs
Flack parameter: 0.033 (5)

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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%.

Computing details top

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: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

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.

catena-Poly[[diiodidomercury(II)]-µ-3-(1-methyl-2-pyrrolidinyl)pyridine- κ²N:N'] top

Crystal data top

[HgI₂(C₁₀H₁₄N₂)]	F(000) = 1096
M_r = 616.62	D_x = 2.980 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2274 reflections
a = 7.7171 (2) Å	θ = 2.1–26.4°
b = 11.1548 (3) Å	µ = 15.67 mm⁻¹
c = 15.9646 (4) Å	T = 123 K
V = 1374.28 (6) Å³	Block, light-yellow
Z = 4	0.20 × 0.16 × 0.12 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2344 independent reflections
Radiation source: fine-focus sealed tube	2274 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→6
T_min = 0.062, T_max = 0.15	k = −13→11
6248 measured reflections	l = −19→15

Refinement top

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)] = 0.023	H-atom parameters constrained
wR(F²) = 0.049	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max = 0.002
2344 reflections	Δρ_max = 0.89 e Å⁻³
137 parameters	Δρ_min = −1.31 e Å⁻³
6 restraints	Absolute structure: Flack (1983), 852 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.033 (5)

Crystal data top

[HgI₂(C₁₀H₁₄N₂)]	V = 1374.28 (6) Å³
M_r = 616.62	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.7171 (2) Å	µ = 15.67 mm⁻¹
b = 11.1548 (3) Å	T = 123 K
c = 15.9646 (4) Å	0.20 × 0.16 × 0.12 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2344 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2274 reflections with I > 2σ(I)
T_min = 0.062, T_max = 0.15	R_int = 0.030
6248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.049	Δρ_max = 0.89 e Å⁻³
S = 0.92	Δρ_min = −1.31 e Å⁻³
2344 reflections	Absolute structure: Flack (1983), 852 Friedel pairs
137 parameters	Absolute structure parameter: 0.033 (5)
6 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.7832 (10)	0.7760 (5)	0.7209 (4)	0.0132 (17)
H1	0.8193	0.7899	0.7770	0.016*
C2	0.6807 (9)	0.6765 (5)	0.7059 (5)	0.0103 (16)
C3	0.6386 (10)	0.6555 (6)	0.6213 (5)	0.0140 (17)
H3	0.5718	0.5874	0.6060	0.017*
C4	0.6952 (10)	0.7348 (6)	0.5605 (5)	0.0179 (18)
H4	0.6661	0.7219	0.5034	0.022*
C5	0.7939 (10)	0.8325 (6)	0.5829 (5)	0.0136 (17)
H5	0.8333	0.8858	0.5406	0.016*
C6	0.6217 (10)	0.5906 (6)	0.7722 (4)	0.0119 (17)
H6	0.5072	0.5572	0.7543	0.014*
C7	0.6751 (11)	0.4290 (6)	0.8612 (5)	0.0188 (19)
H7A	0.7662	0.3799	0.8882	0.023*
H7B	0.5756	0.3766	0.8474	0.023*
C8	0.6183 (11)	0.5305 (6)	0.9193 (4)	0.0185 (19)
H8A	0.7063	0.5453	0.9633	0.022*
H8B	0.5063	0.5115	0.9465	0.022*
C9	0.6006 (10)	0.6397 (6)	0.8611 (4)	0.0140 (17)
H9A	0.4857	0.6778	0.8681	0.017*
H9B	0.6915	0.6998	0.8735	0.017*
C10	0.7411 (11)	0.4025 (6)	0.7151 (5)	0.023 (2)
H10A	0.7971	0.3277	0.7324	0.034*
H10B	0.8038	0.4368	0.6674	0.034*
H10C	0.6210	0.3861	0.6988	0.034*
Hg1	0.95797 (4)	1.05075 (2)	0.698176 (18)	0.01298 (8)
I1	0.84450 (6)	1.06434 (4)	0.85667 (3)	0.01766 (13)
I2	0.91255 (7)	1.16336 (4)	0.55341 (3)	0.02021 (14)
N1	0.8355 (8)	0.8542 (4)	0.6627 (4)	0.0104 (14)
N2	0.7431 (9)	0.4874 (4)	0.7847 (3)	0.0126 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.016 (4)	0.017 (3)	0.007 (4)	−0.001 (3)	−0.002 (3)	0.008 (3)
C2	0.010 (2)	0.011 (2)	0.010 (2)	0.0016 (17)	0.0016 (17)	−0.0009 (17)
C3	0.011 (4)	0.016 (3)	0.016 (5)	0.001 (3)	−0.005 (3)	−0.001 (3)
C4	0.019 (5)	0.022 (4)	0.012 (5)	0.005 (4)	−0.007 (4)	0.000 (4)
C5	0.014 (4)	0.022 (4)	0.005 (4)	0.007 (4)	−0.001 (3)	0.002 (3)
C6	0.010 (4)	0.014 (3)	0.012 (4)	0.001 (3)	−0.001 (3)	0.002 (3)
C7	0.028 (5)	0.018 (4)	0.011 (4)	0.001 (4)	0.008 (4)	0.003 (3)
C8	0.024 (5)	0.021 (4)	0.011 (4)	−0.003 (4)	0.006 (4)	−0.001 (3)
C9	0.020 (4)	0.016 (3)	0.007 (4)	0.004 (3)	0.005 (3)	−0.001 (3)
C10	0.023 (5)	0.017 (4)	0.029 (6)	−0.001 (4)	0.002 (4)	−0.006 (4)
Hg1	0.01563 (16)	0.01506 (14)	0.00825 (16)	−0.00253 (13)	−0.00074 (12)	0.00158 (13)
I1	0.0168 (3)	0.0258 (3)	0.0105 (3)	−0.0004 (2)	0.0026 (2)	−0.0031 (2)
I2	0.0254 (3)	0.0222 (3)	0.0131 (3)	−0.0003 (2)	−0.0033 (2)	0.0079 (2)
N1	0.015 (3)	0.010 (3)	0.006 (3)	−0.003 (3)	0.002 (3)	0.002 (3)
N2	0.021 (4)	0.007 (3)	0.009 (4)	−0.005 (3)	0.002 (3)	0.003 (3)

Geometric parameters (Å, º) top

C1—N1	1.336 (8)	C7—H7A	0.9900
C1—C2	1.384 (9)	C7—H7B	0.9900
C1—H1	0.9500	C8—C9	1.538 (9)
C2—C3	1.409 (9)	C8—H8A	0.9900
C2—C6	1.499 (9)	C8—H8B	0.9900
C3—C4	1.384 (9)	C9—H9A	0.9900
C3—H3	0.9500	C9—H9B	0.9900
C4—C5	1.376 (9)	C10—N2	1.460 (8)
C4—H4	0.9500	C10—H10A	0.9800
C5—N1	1.336 (9)	C10—H10B	0.9800
C5—H5	0.9500	C10—H10C	0.9800
C6—N2	1.498 (8)	Hg1—N2ⁱ	2.428 (7)
C6—C9	1.530 (9)	Hg1—N1	2.454 (5)
C6—H6	1.0000	Hg1—I2	2.6536 (5)
C7—N2	1.481 (9)	Hg1—I1	2.6819 (6)
C7—C8	1.528 (9)	N2—Hg1ⁱⁱ	2.428 (7)

N1—C1—C2	125.1 (7)	C7—C8—H8B	110.9
N1—C1—H1	117.4	C9—C8—H8B	110.9
C2—C1—H1	117.4	H8A—C8—H8B	108.9
C1—C2—C3	115.5 (6)	C6—C9—C8	105.5 (5)
C1—C2—C6	124.3 (7)	C6—C9—H9A	110.6
C3—C2—C6	120.1 (6)	C8—C9—H9A	110.6
C4—C3—C2	119.5 (6)	C6—C9—H9B	110.6
C4—C3—H3	120.2	C8—C9—H9B	110.6
C2—C3—H3	120.2	H9A—C9—H9B	108.8
C5—C4—C3	119.9 (7)	N2—C10—H10A	109.5
C5—C4—H4	120.0	N2—C10—H10B	109.5
C3—C4—H4	120.0	H10A—C10—H10B	109.5
N1—C5—C4	121.6 (7)	N2—C10—H10C	109.5
N1—C5—H5	119.2	H10A—C10—H10C	109.5
C4—C5—H5	119.2	H10B—C10—H10C	109.5
N2—C6—C2	113.2 (6)	N2ⁱ—Hg1—N1	97.59 (19)
N2—C6—C9	102.6 (5)	N2ⁱ—Hg1—I2	111.18 (13)
C2—C6—C9	117.3 (6)	N1—Hg1—I2	99.85 (13)
N2—C6—H6	107.7	N2ⁱ—Hg1—I1	102.73 (13)
C2—C6—H6	107.7	N1—Hg1—I1	98.19 (13)
C9—C6—H6	107.7	I2—Hg1—I1	138.749 (19)
N2—C7—C8	106.1 (5)	C1—N1—C5	118.2 (6)
N2—C7—H7A	110.5	C1—N1—Hg1	122.6 (4)
C8—C7—H7A	110.5	C5—N1—Hg1	118.3 (4)
N2—C7—H7B	110.5	C10—N2—C7	109.8 (5)
C8—C7—H7B	110.5	C10—N2—C6	113.0 (6)
H7A—C7—H7B	108.7	C7—N2—C6	103.1 (5)
C7—C8—C9	104.2 (6)	C10—N2—Hg1ⁱⁱ	106.5 (5)
C7—C8—H8A	110.9	C7—N2—Hg1ⁱⁱ	111.8 (5)
C9—C8—H8A	110.9	C6—N2—Hg1ⁱⁱ	112.7 (4)

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

Experimental details

Crystal data
Chemical formula	[HgI₂(C₁₀H₁₄N₂)]
M_r	616.62
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	123
a, b, c (Å)	7.7171 (2), 11.1548 (3), 15.9646 (4)
V (Å³)	1374.28 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	15.67
Crystal size (mm)	0.20 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.062, 0.15
No. of measured, independent and observed [I > 2σ(I)] reflections	6248, 2344, 2274
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.049, 0.92
No. of reflections	2344
No. of parameters	137
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −1.31
Absolute structure	Flack (1983), 852 Friedel pairs
Absolute structure parameter	0.033 (5)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Acknowledgements

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

References

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