catena-Poly[[dibromidomercury(II)]-μ-3-(1-methyl­pyrrolidin-2-yl)pyridine-κ2N:N′]

Jiang, Z.; Tang, G.; Zhang, Y.; Zhao, J.

doi:10.1107/S1600536808030055

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1319

doi:10.1107/S1600536808030055

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catena-Poly[[dibromidomercury(II)]-μ-3-(1-methylpyrrolidin-2-yl)pyridine-κ²N:N′]

Zhengjing Jiang,^a,^b Guodong Tang,^a,^b Yu Zhang ^a ^* and Jianying Zhao ^a

^aDepartment of Chemistry, Huaiyin Teachers College, Huai'an 223300, Jiangsu, People's Republic of China, and ^bKey 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
^*Correspondence e-mail: yuzhang@hytc.edu.cn

(Received 10 September 2008; accepted 18 September 2008; online 24 September 2008)

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.

Related literature

For other nicotine complexes of copper and mercury, see: Meyer et al. (2006 ); Haendler (1990 ). For the isostructural dichlorido(nicotine)mercury(II) chain polymer complex, see: Udupa & Krebs (1980 );

Experimental

Crystal data

[HgBr₂(C₁₀H₁₄N₂)]
M_r = 522.64
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.6306 (9) Å
b = 11.2177 (14) Å
c = 15.443 (2) Å
V = 1321.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 17.66 mm⁻¹
T = 296 (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 = 0.153 (expected range = 0.049–0.120)
10476 measured reflections
2601 independent reflections
2137 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.076
S = 1.00
2601 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 1.44 e Å⁻³
Δρ_min = −1.03 e Å⁻³
Absolute structure: Flack, (1983 ), 1083 Friedel pairs
Flack parameter: −0.006 (16)

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030055/si2110sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030055/si2110Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For nicotine complexes, see: Meyer et al., (2006); Haendler, (1990). For the isostructural dichlorido(nicotine)mercury(II) chain polymer complex, see: Udupa & Krebs, (1980);

Experimental top

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%.

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: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXL9 (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[[dibromidomercury(II)]-µ-3-(1-methylpyrrolidin-2-yl)pyridine- κ²N:N'] top

Crystal data top

[HgBr₂(C₁₀H₁₄N₂)]	F(000) = 952
M_r = 522.64	D_x = 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

Data collection top

Bruker SMART APEXII CCD diffractometer	2601 independent reflections
Radiation source: fine-focus sealed tube	2137 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→9
T_min = 0.062, T_max = 0.153	k = −13→13
10476 measured reflections	l = −19→16

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)] = 0.039	H-atom parameters constrained
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0314P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2601 reflections	Δρ_max = 1.44 e Å⁻³
137 parameters	Δρ_min = −1.03 e Å⁻³
0 restraints	Absolute structure: Flack, (1983), 1083 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.006 (16)

Crystal data top

[HgBr₂(C₁₀H₁₄N₂)]	V = 1321.9 (3) Å³
M_r = 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

Data collection top

Bruker SMART APEXII CCD diffractometer	2601 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2137 reflections with I > 2σ(I)
T_min = 0.062, T_max = 0.153	R_int = 0.057
10476 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.076	Δρ_max = 1.44 e Å⁻³
S = 1.00	Δρ_min = −1.03 e Å⁻³
2601 reflections	Absolute structure: Flack, (1983), 1083 Friedel pairs
137 parameters	Absolute structure parameter: −0.006 (16)
0 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
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	[HgBr₂(C₁₀H₁₄N₂)]
M_r	522.64
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	7.6306 (9), 11.2177 (14), 15.443 (2)
V (Å³)	1321.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	17.66
Crystal size (mm)	0.20 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.062, 0.153
No. of measured, independent and observed [I > 2σ(I)] reflections	10476, 2601, 2137
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.076, 1.00
No. of reflections	2601
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.44, −1.03
Absolute structure	Flack, (1983), 1083 Friedel pairs
Absolute structure parameter	−0.006 (16)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL9 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Acknowledgements

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.

References

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