catena-Poly[[di­chlorido­mercury(II)]-μ-3,5-bis­[2-(pyridin-4-yl)ethyn­yl]pyridine-κ2N:N′]

Zhang, P.; Yang, Q.; Zhao, M.

doi:10.1107/S2414314616019519

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161951

https://doi.org/10.1107/S2414314616019519

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catena-Poly[[dichloridomercury(II)]-μ-3,5-bis[2-(pyridin-4-yl)ethynyl]pyridine-κ²N:N′]

Peng Zhang,^a Qi Yang ^a and Minjian Zhao ^a ^*

^aBeijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, People's Republic of China
^*Correspondence e-mail: wangbin_01@yeah.net

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 28 November 2016; accepted 6 December 2016; online 9 December 2016)

In the title coordination polymer, [HgCl₂(C₁₉H₁₁N₃)]_n, the Hg^II atom is coordinated by two N atoms of symmetry-related 3,5-bis(pyridin-4-ylethynyl)pyridine ligands (L) and by two chloride ions in a distorted tetrahedral geometry. The dihedral angles between the coordinated pyridine rings and the central pyridine ring are 44.6 (3) and 14.2 (3)°, respectively, while the dihedral angle between the two coordinating pyridine rings is 56.1 (3)°. The ligand bridges the Hg^II atoms, forming a zigzag chain running parallel to the b axis. There are no other significant intermolecular interactions present in the crystal.

Keywords: crystal structure; angular pyridyl-based ligand; Hg^II; coordination polymer; zigzag chain.

CCDC reference: 1520979

Structure description

Coordination polymers (CPs) have attracted much attention because of their fascinating architectures and intriguing topologies as well as their potential applications in catalysis, adsorption, separation, and luminescence. Pyridine-based ligands are widely used in the construction of CPs, most of which are constructed from linear ligands. However, CPs assembled from angular pyridyl-based ligands are relatively rare.

In this work, an angular pyridyl-based ligand, 3,5-bis(pyridin-4-ylethynyl)pyridine (L), was employed to react with HgCl₂ to afford the title coordination polymer, illustrated in Fig. 1. The Hg^II atom, Hg1, is coordinated by two N atoms, N1 and N3, of two symmetry-related L ligands and two chloride ions in a distorted tetrahedral geometry (Table 1 and Fig. 1). The τ₄ descriptor for fourfold coordination = 0.33 (extreme forms: 0.00 for square-planar and 1.00 for tetrahedral; Yang et al., 2007 )

Table 1
Selected geometric parameters (Å, °)

Hg1—Cl2	2.3508 (16)	Hg1—N3ⁱ	2.420 (5)
Hg1—Cl1	2.3623 (16)	Hg1—N1	2.441 (5)

Cl2—Hg1—Cl1	156.83 (6)	Cl2—Hg1—N1	97.54 (13)
Cl2—Hg1—N3ⁱ	99.51 (12)	Cl1—Hg1—N1	96.90 (13)
Cl1—Hg1—N3ⁱ	97.04 (13)	N3ⁱ—Hg1—N1	95.45 (16)
Symmetry code: (i) $[-x-2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
The coordination mode of the title complex, with the atom labelling [symmetry codes: (#1) −x − 2, y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (#2) −x − 2, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ]. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.

The dihedral angles between the coordinated pyridine rings (N1/C1–C5 and N3/C15–C19) and the central pyridine ring (N2/C8–C12) are 44.6 (3) and 14.2 (3)°, respectively, and the dihedral angle between the two coordinating pyridine rings is 56.1 (3)°. The ligands bridge the mercury atoms, forming a zigzag chain running parallel to the b axis (Fig. 2). There are no other significant intermolecular interactions present in the crystal.

Figure 2
A view along the b axis of the zigzag chain structure of the title coordination polymer. Displacement ellipsoids are drawn at the 50% probability level, and H atoms have been omitted for clarity.

The linear pyridyl-based ligand, 1,4-bis(pyridin-4-ylethynyl)benzene, has also been used to form a similar zigzag coordination polymer with HgCl₂ (Wang et al., 2014 ).

Synthesis and crystallization

The organic ligand 3,5-bis(pyridin-4-ylethynyl)pyridine (L) was synthesized from the reaction between 3,5-dibromopyridine and 4-ethynylpyridine hydrochloride following the reported procedure (Yamamoto et al., 2003 ). To synthesise the title coordination polymer, a 3 ml methanol solution of HgCl₂ (0.1 mmol, 27 mg) was layered onto a 3 ml chloroform solution of L (0.2 mmol, 56 mg). After three days, colourless crystals of the title coordination polymer were obtained.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The maximum and minimum residual electron density peaks of 1.81 and −1.42 e Å⁻³, respectively, are located at ca 1.00 Å from the Hg atom.

Table 2
Experimental details

Crystal data
Chemical formula	[HgCl₂(C₁₉H₁₁Cl₂N₃)]
M_r	552.80
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	5.0941 (10), 22.946 (5), 15.831 (3)
β (°)	96.229 (4)
V (Å³)	1839.5 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	8.66
Crystal size (mm)	0.18 × 0.16 × 0.16

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998 )
T_min, T_max	0.305, 0.338
No. of measured, independent and observed [I > 2σ(I)] reflections	9673, 3224, 2631
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.079, 0.97
No. of reflections	3224
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.81, −1.43
Computer programs: SMART and SAINT (Bruker, 1998), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1520979

Crystal structure: contains datablocks 1, I. DOI: https://doi.org/10.1107/S2414314616019519/su4103sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019519/su4103Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616019519/su4103Isup3.cdx

checkCIF report

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

catena-Poly[[dichloridomercury(II)]-µ-3,5-bis[2-(pyridin-4-yl)ethynyl]pyridine-κ²N:N'] top

Crystal data top

[HgCl₂(C₁₉H₁₁N₃)]	F(000) = 1040
M_r = 552.80	D_x = 1.996 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2134 reflections
a = 5.0941 (10) Å	θ = 3.6–25.0°
b = 22.946 (5) Å	µ = 8.66 mm⁻¹
c = 15.831 (3) Å	T = 173 K
β = 96.229 (4)°	Block, colourless
V = 1839.5 (6) Å³	0.18 × 0.16 × 0.16 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3224 independent reflections
Radiation source: fine-focus sealed tube	2631 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω and phi scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −5→6
T_min = 0.305, T_max = 0.338	k = −27→27
9673 measured reflections	l = −18→11

Refinement top

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0469P)²] where P = (F_o² + 2F_c²)/3
3224 reflections	(Δ/σ)_max = 0.002
226 parameters	Δρ_max = 1.81 e Å⁻³
0 restraints	Δρ_min = −1.43 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Hg1	0.44656 (4)	0.513510 (10)	0.762796 (15)	0.02213 (10)
Cl2	0.5910 (3)	0.44510 (7)	0.86826 (10)	0.0285 (4)
Cl1	0.4855 (3)	0.58105 (7)	0.65222 (10)	0.0289 (4)
N1	0.0952 (9)	0.4547 (2)	0.6882 (3)	0.0253 (12)
C5	0.0249 (12)	0.4028 (3)	0.7178 (4)	0.0283 (15)
H5	0.1159	0.3886	0.7677	0.034*
C14	−1.5891 (11)	0.1642 (3)	0.5383 (4)	0.0232 (14)
C16	−1.9249 (11)	0.0862 (3)	0.5394 (4)	0.0227 (13)
H16	−1.8960	0.0752	0.4847	0.027*
C8	−0.8904 (11)	0.2939 (2)	0.4708 (4)	0.0203 (13)
N3	−2.1573 (9)	0.0714 (2)	0.6592 (3)	0.0202 (11)
C13	−1.4324 (11)	0.1912 (3)	0.5042 (4)	0.0236 (14)
C12	−1.0721 (10)	0.2621 (2)	0.5116 (4)	0.0210 (13)
H12	−1.0797	0.2661	0.5697	0.025*
C1	−0.0400 (11)	0.4744 (3)	0.6168 (4)	0.0252 (14)
H1	0.0040	0.5106	0.5959	0.030*
C9	−0.8887 (12)	0.2864 (3)	0.3838 (4)	0.0283 (15)
H9	−0.7668	0.3077	0.3567	0.034*
N2	−1.0527 (10)	0.2503 (2)	0.3359 (3)	0.0338 (14)
C7	−0.6965 (11)	0.3303 (3)	0.5187 (4)	0.0262 (14)
C17	−2.1085 (11)	0.0572 (3)	0.5815 (4)	0.0234 (14)
H17	−2.2017	0.0265	0.5542	0.028*
C4	−0.1776 (12)	0.3696 (3)	0.6770 (4)	0.0294 (15)
H4	−0.2199	0.3337	0.6991	0.035*
C11	−1.2422 (11)	0.2241 (3)	0.4638 (4)	0.0215 (13)
C10	−1.2246 (12)	0.2200 (3)	0.3777 (4)	0.0324 (16)
H10	−1.3391	0.1945	0.3463	0.039*
C19	−1.8426 (12)	0.1472 (3)	0.6601 (4)	0.0302 (15)
H19	−1.7571	0.1784	0.6887	0.036*
C18	−2.0270 (12)	0.1161 (3)	0.6974 (4)	0.0283 (15)
H18	−2.0630	0.1266	0.7518	0.034*
C15	−1.7825 (11)	0.1325 (3)	0.5794 (4)	0.0211 (13)
C2	−0.2419 (12)	0.4432 (3)	0.5727 (4)	0.0290 (15)
H2	−0.3273	0.4582	0.5224	0.035*
C3	−0.3178 (11)	0.3903 (3)	0.6024 (4)	0.0240 (14)
C6	−0.5281 (11)	0.3577 (3)	0.5586 (4)	0.0253 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.02305 (14)	0.02195 (16)	0.02119 (16)	−0.00100 (10)	0.00146 (9)	−0.00379 (10)
Cl2	0.0322 (8)	0.0272 (8)	0.0249 (9)	0.0067 (6)	−0.0021 (6)	−0.0016 (7)
Cl1	0.0368 (8)	0.0263 (8)	0.0238 (9)	−0.0080 (7)	0.0041 (6)	0.0005 (7)
N1	0.022 (3)	0.029 (3)	0.027 (3)	0.002 (2)	0.008 (2)	−0.004 (2)
C5	0.034 (4)	0.029 (4)	0.021 (4)	−0.002 (3)	0.001 (3)	−0.002 (3)
C14	0.020 (3)	0.020 (3)	0.029 (4)	0.003 (3)	−0.002 (3)	0.003 (3)
C16	0.026 (3)	0.020 (3)	0.024 (4)	0.000 (3)	0.009 (3)	−0.001 (3)
C8	0.018 (3)	0.017 (3)	0.026 (4)	0.002 (2)	0.000 (2)	0.003 (3)
N3	0.023 (3)	0.017 (3)	0.019 (3)	0.002 (2)	−0.001 (2)	0.006 (2)
C13	0.022 (3)	0.025 (3)	0.023 (4)	−0.004 (3)	−0.001 (3)	0.000 (3)
C12	0.022 (3)	0.018 (3)	0.023 (4)	0.007 (3)	0.003 (2)	0.002 (3)
C1	0.020 (3)	0.022 (3)	0.033 (4)	0.001 (2)	0.003 (3)	0.006 (3)
C9	0.026 (3)	0.029 (4)	0.030 (4)	−0.004 (3)	−0.001 (3)	0.004 (3)
N2	0.039 (3)	0.035 (3)	0.027 (4)	−0.015 (3)	−0.001 (2)	0.004 (3)
C7	0.022 (3)	0.023 (3)	0.034 (4)	0.004 (3)	0.006 (3)	−0.003 (3)
C17	0.025 (3)	0.019 (3)	0.026 (4)	0.000 (2)	−0.001 (3)	−0.001 (3)
C4	0.033 (4)	0.029 (4)	0.028 (4)	−0.011 (3)	0.009 (3)	−0.003 (3)
C11	0.019 (3)	0.020 (3)	0.025 (4)	0.005 (2)	0.001 (2)	0.002 (3)
C10	0.033 (4)	0.030 (4)	0.031 (4)	−0.012 (3)	−0.006 (3)	0.001 (3)
C19	0.035 (4)	0.032 (4)	0.023 (4)	−0.010 (3)	−0.003 (3)	0.001 (3)
C18	0.035 (4)	0.030 (4)	0.019 (4)	−0.004 (3)	0.000 (3)	0.000 (3)
C15	0.017 (3)	0.025 (3)	0.021 (4)	0.004 (2)	−0.001 (2)	0.009 (3)
C2	0.027 (3)	0.030 (4)	0.028 (4)	0.002 (3)	−0.006 (3)	−0.001 (3)
C3	0.021 (3)	0.023 (3)	0.029 (4)	−0.004 (3)	0.010 (2)	−0.009 (3)
C6	0.023 (3)	0.025 (4)	0.029 (4)	−0.004 (3)	0.009 (3)	−0.009 (3)

Geometric parameters (Å, º) top

Hg1—Cl2	2.3508 (16)	N3—C18	1.332 (8)
Hg1—Cl1	2.3623 (16)	N3—Hg1ⁱⁱ	2.420 (5)
Hg1—N3ⁱ	2.420 (5)	C13—C11	1.433 (8)
Hg1—N1	2.441 (5)	C12—C11	1.392 (8)
N1—C1	1.338 (8)	C1—C2	1.379 (8)
N1—C5	1.343 (8)	C9—N2	1.350 (8)
C5—C4	1.385 (8)	N2—C10	1.346 (8)
C14—C13	1.185 (9)	C7—C6	1.188 (8)
C14—C15	1.437 (9)	C4—C3	1.395 (9)
C16—C17	1.377 (8)	C11—C10	1.380 (9)
C16—C15	1.397 (8)	C19—C18	1.364 (9)
C8—C9	1.389 (9)	C19—C15	1.387 (9)
C8—C12	1.391 (9)	C2—C3	1.373 (9)
C8—C7	1.445 (8)	C3—C6	1.424 (8)
N3—C17	1.323 (8)

Cl2—Hg1—Cl1	156.83 (6)	N1—C1—C2	122.7 (6)
Cl2—Hg1—N3ⁱ	99.51 (12)	N2—C9—C8	124.2 (6)
Cl1—Hg1—N3ⁱ	97.04 (13)	C10—N2—C9	116.0 (6)
Cl2—Hg1—N1	97.54 (13)	C6—C7—C8	176.4 (6)
Cl1—Hg1—N1	96.90 (13)	N3—C17—C16	122.4 (6)
N3ⁱ—Hg1—N1	95.45 (16)	C5—C4—C3	119.6 (6)
C1—N1—C5	117.5 (5)	C10—C11—C12	118.4 (6)
C1—N1—Hg1	120.4 (4)	C10—C11—C13	121.6 (5)
C5—N1—Hg1	122.1 (4)	C12—C11—C13	120.0 (6)
N1—C5—C4	122.6 (6)	N2—C10—C11	124.4 (6)
C13—C14—C15	178.9 (7)	C18—C19—C15	120.2 (6)
C17—C16—C15	119.7 (6)	N3—C18—C19	122.6 (7)
C9—C8—C12	118.1 (5)	C19—C15—C16	116.6 (6)
C9—C8—C7	121.0 (6)	C19—C15—C14	121.6 (6)
C12—C8—C7	120.7 (6)	C16—C15—C14	121.8 (6)
C17—N3—C18	118.6 (6)	C3—C2—C1	120.5 (6)
C17—N3—Hg1ⁱⁱ	121.7 (4)	C2—C3—C4	117.0 (5)
C18—N3—Hg1ⁱⁱ	119.5 (4)	C2—C3—C6	121.5 (6)
C14—C13—C11	179.3 (7)	C4—C3—C6	121.5 (6)
C8—C12—C11	118.8 (6)	C7—C6—C3	176.8 (7)

Cl2—Hg1—N1—C1	−175.5 (5)	C8—C12—C11—C13	−179.6 (5)
Cl1—Hg1—N1—C1	−13.7 (5)	C14—C13—C11—C10	−171 (100)
N3ⁱ—Hg1—N1—C1	84.1 (5)	C14—C13—C11—C12	8 (66)
Cl2—Hg1—N1—C5	6.4 (5)	C9—N2—C10—C11	0.5 (10)
Cl1—Hg1—N1—C5	168.2 (5)	C12—C11—C10—N2	0.0 (10)
N3ⁱ—Hg1—N1—C5	−94.0 (5)	C13—C11—C10—N2	179.2 (6)
C1—N1—C5—C4	0.5 (10)	C17—N3—C18—C19	−1.0 (9)
Hg1—N1—C5—C4	178.7 (5)	Hg1ⁱⁱ—N3—C18—C19	173.8 (5)
C15—C14—C13—C11	77 (79)	C15—C19—C18—N3	−0.6 (10)
C9—C8—C12—C11	0.4 (8)	C18—C19—C15—C16	1.9 (9)
C7—C8—C12—C11	−175.2 (5)	C18—C19—C15—C14	−179.9 (6)
C5—N1—C1—C2	−1.1 (10)	C17—C16—C15—C19	−1.7 (8)
Hg1—N1—C1—C2	−179.4 (5)	C17—C16—C15—C14	−179.9 (5)
C12—C8—C9—N2	0.1 (9)	C13—C14—C15—C19	−71 (37)
C7—C8—C9—N2	175.6 (6)	C13—C14—C15—C16	107 (37)
C8—C9—N2—C10	−0.5 (9)	N1—C1—C2—C3	1.7 (11)
C9—C8—C7—C6	−86 (12)	C1—C2—C3—C4	−1.6 (10)
C12—C8—C7—C6	89 (12)	C1—C2—C3—C6	179.1 (6)
C18—N3—C17—C16	1.2 (9)	C5—C4—C3—C2	1.0 (9)
Hg1ⁱⁱ—N3—C17—C16	−173.5 (4)	C5—C4—C3—C6	−179.7 (6)
C15—C16—C17—N3	0.2 (9)	C8—C7—C6—C3	70 (19)
N1—C5—C4—C3	−0.4 (10)	C2—C3—C6—C7	62 (12)
C8—C12—C11—C10	−0.4 (8)	C4—C3—C6—C7	−117 (12)

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

Acknowledgements

The authors thank Beijing University of Technology for supporting this work.

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