catena-Poly[[μ2-4,4′-bis­(pyridin-3-ylethyn­yl)-1,1′-biphenyl-κ2N:N′]bis­(μ2-thio­cyanato-κ2N:S)bis­(thio­cyanato-κS)dimercury(II)]

Tan, S.; Liu, L.; Du, Y.

doi:10.1107/S2414314617000591

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x170059

https://doi.org/10.1107/S2414314617000591

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catena-Poly[[μ₂-4,4′-bis(pyridin-3-ylethynyl)-1,1′-biphenyl-κ²N:N′]bis(μ₂-thiocyanato-κ²N:S)bis(thiocyanato-κS)dimercury(II)]

Shuzhi Tan,^a ^* Leili Liu ^a and Yongli Du ^a

^aSchool of Chemistry and Pharmaceutical Engineering, Qilu University of Technology, Jinan, Shandong 250353, People's Republic of China
^*Correspondence e-mail: cyrstalclear@126.com

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 13 December 2016; accepted 12 January 2017; online 17 January 2017)

In the title polymer, [Hg₂(SCN)₄(C₂₆H₁₆N₂)]_n, the two equivalent Hg^II atoms are coordinated by one N atom of a bridging 4,4′-bis(pyridin-3-ylethynyl)-1,1′-biphenyl ligand, two S atoms of two thiocyanates and one N atom of a thiocyanate, giving rise to a distored tetrahedral coordination environment. Two thiocyanate ligands bridge symmetry-related metal atoms to form a polymeric chain extending parallel to [001], and another bridging mode is accomplished by the organic ligand that is located about an inversion centre. The dihedral angle between the coordinating pyridine ring and the benzene ring is 11.4 (2)°, and the two coordinating pyridine rings in the organic ligand are parallel by symmetry. The point group of the ligand in the compound is thus close to C_2h. The result of the mode of the organic ligands is the formation of zigzag sheets connected via bridging thiocyanate ligands.

Keywords: crystal structure; inorganic polymer; thiocyanate.

CCDC reference: 1526974

Structure description

Recently, coordination polymers (CPs) have attracted much attention due to their fascinating structures as well as their potential applications in gas storage and separation, heterogeneous catalysis, proton conductivity, and luminescent sensors, etc. Organic ligands play a key role in the construction of CPs with various structures and topologies with pyridine-based ligands being widely used. A mercury-based coordination polymer was described by Wang et al. (2014 ).

In this work, an angular pyridine-based ligand, 4,4′-bis(pyridin-3-ylethynyl)-1,1′-biphenyl (L) was synthesized and employed to react with Hg(SCN)₂ to afford the title complex, [Hg₂(SCN)₄(L)]_n. The Hg^II atom is coordinated by one N atom of an L ligand, two S atoms of two thiocyanate ligands (one bridging, one terminal) and one N atom of the another bridging thiocyanate ligand, in a distorted tetrahedral environment (Table 1 and Fig. 1). The dihedral angle between the coordinating pyridine ring and the benzene ring is 11.4 (2)°, and the two coordinating pyridine rings are parallel, by symmetry. The formed inorganic [Hg(SCN)₂]_n chains are bridged by the organic ligands into a three-dimensional network, whereby the organic ligands are arranged in zigzag sheets approximately parallel to (010) (Fig. 2). Within an organic sheet π–π interactions between nearly parallel aligned pyridine and benzene rings of neighbouring ligands are evident, with a centroid-to-centroid distance of 3.655 (3) Å.

Table 1
Selected geometric parameters (Å, °)

Hg1—N1	2.392 (4)	Hg1—S2ⁱ	2.4325 (13)
Hg1—S1	2.4170 (13)	Hg1—N2	2.568 (5)

N1—Hg1—S1	109.28 (10)	N1—Hg1—N2	84.04 (13)
N1—Hg1—S2ⁱ	99.19 (10)	S1—Hg1—N2	98.29 (10)
S1—Hg1—S2ⁱ	148.61 (5)	S2ⁱ—Hg1—N2	97.50 (11)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The coordination mode of the title complex, with displacement ellipsoids drawn at the 50% probability level. All H atoms have been omitted for clarity. [Symmetry codes: (i) −2 − x, 1 − y, −z; (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ .]

Figure 2
The zigzag sheets of the complex, viewed down the c axis, with displacement ellipsoids drawn at the 50% probability level. All H atoms have been omitted for clarity.

Synthesis and crystallization

The organic ligand L, 4,4′-bis(pyridin-3-ylethynyl)-1,1′-biphenyl, was synthesized following the reported procedure (Kaae et al., 2012 ). 3 ml of a methanol solution of Hg(SCN)₂ (0.1 mmol, 31 mg) was layered upon 3 ml of a chloroform solution of L (0.2 mmol, 70 mg). After 4 d, yellow crystals of the title complex suitable for X-ray analysis 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 2.15 and 1.73 e Å⁻³, respectively, are located 0.93 and 1.00 Å from the Hg atom.

Table 2
Experimental details

Crystal data
Chemical formula	[Hg₂(SCN)₄(C₂₆H₁₆N₂)]
M_r	989.9
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.9175 (5), 17.6267 (13), 12.0029 (9)
β (°)	91.017 (1)
V (Å³)	1463.32 (19)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	10.80
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998 )
T_min, T_max	0.221, 0.247
No. of measured, independent and observed [I > 2σ(I)] reflections	7862, 2726, 2275
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.062, 1.02
No. of reflections	2726
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.52, −0.78
Computer programs: SMART and SAINT (Bruker, 1998), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2016/6 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1526974

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617000591/bh4022sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617000591/bh4022Isup2.hkl

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: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2016/6 (Sheldrick, 2015).

catena-Poly[[µ₂-4,4'-bis(pyridin-3-ylethynyl)-1,1'-biphenyl-κ²N:N']bis(µ₂-thiocyanato-κ²N:S)bis(thiocyanato-κS)dimercury(II)] top

Crystal data top

[Hg₂(SCN)₄(C₂₆H₁₆N₂)]	F(000) = 924
M_r = 989.9	D_x = 2.247 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.9175 (5) Å	Cell parameters from 2275 reflections
b = 17.6267 (13) Å	θ = 2.1–25.5°
c = 12.0029 (9) Å	µ = 10.80 mm⁻¹
β = 91.017 (1)°	T = 100 K
V = 1463.32 (19) Å³	Block, yellow
Z = 2	0.20 × 0.18 × 0.18 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2275 reflections with I > 2σ(I)
ω and phi scans	R_int = 0.030
Absorption correction: multi-scan (SADABS; Bruker, 1998)	θ_max = 25.5°, θ_min = 2.1°
T_min = 0.221, T_max = 0.247	h = −8→8
7862 measured reflections	k = −20→21
2726 independent reflections	l = −10→14

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0265P)² + 1.8001P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
2726 reflections	Δρ_max = 1.52 e Å⁻³
190 parameters	Δρ_min = −0.78 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
Hg1	0.34026 (3)	0.25411 (2)	0.44910 (2)	0.01732 (8)
S1	0.65961 (18)	0.27179 (8)	0.52991 (12)	0.0205 (3)
S2	0.1157 (2)	0.32566 (8)	0.84385 (12)	0.0227 (3)
N1	0.1994 (6)	0.3753 (2)	0.4098 (3)	0.0156 (9)
N2	0.1456 (6)	0.2626 (2)	0.6289 (4)	0.0192 (10)
N3	0.5993 (7)	0.2468 (3)	0.7608 (4)	0.0295 (12)
C1	0.3013 (7)	0.4384 (3)	0.4306 (5)	0.0204 (12)
H1	0.425505	0.433605	0.464884	0.025*
C2	0.2349 (8)	0.5101 (3)	0.4046 (5)	0.0248 (13)
H2	0.311575	0.553457	0.421443	0.030*
C3	0.0562 (7)	0.5181 (3)	0.3540 (5)	0.0214 (12)
H3	0.007957	0.567035	0.335333	0.026*
C4	−0.0549 (7)	0.4526 (3)	0.3300 (4)	0.0163 (11)
C5	0.0234 (7)	0.3833 (3)	0.3607 (4)	0.0182 (11)
H5	−0.050779	0.338861	0.346461	0.022*
C6	−0.2388 (7)	0.4581 (3)	0.2727 (4)	0.0182 (12)
C7	−0.3830 (7)	0.4664 (3)	0.2206 (5)	0.0189 (12)
C8	−0.5611 (7)	0.4759 (3)	0.1569 (4)	0.0143 (11)
C9	−0.6090 (7)	0.5459 (3)	0.1106 (5)	0.0185 (12)
H9	−0.524889	0.587946	0.121710	0.022*
C10	−0.7775 (7)	0.5550 (3)	0.0487 (4)	0.0147 (11)
H10	−0.805817	0.602942	0.016040	0.018*
C11	−0.9079 (7)	0.4947 (3)	0.0330 (4)	0.0145 (11)
C12	−0.8575 (7)	0.4249 (3)	0.0807 (4)	0.0159 (11)
H12	−0.943342	0.383226	0.071779	0.019*
C13	−0.6881 (7)	0.4148 (3)	0.1398 (4)	0.0175 (11)
H13	−0.656548	0.366182	0.169164	0.021*
C14	0.6192 (8)	0.2577 (3)	0.6661 (5)	0.0211 (12)
C15	0.1390 (7)	0.2870 (3)	0.7177 (5)	0.0169 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.01973 (12)	0.01986 (12)	0.01214 (12)	0.00123 (9)	−0.00573 (8)	0.00026 (9)
S1	0.0173 (6)	0.0301 (7)	0.0139 (7)	−0.0010 (6)	−0.0030 (6)	0.0026 (6)
S2	0.0288 (7)	0.0258 (7)	0.0135 (7)	0.0112 (6)	−0.0051 (6)	−0.0039 (6)
N1	0.015 (2)	0.021 (2)	0.010 (2)	−0.0006 (17)	−0.0049 (19)	−0.0024 (18)
N2	0.019 (2)	0.022 (2)	0.016 (3)	0.0052 (18)	−0.004 (2)	0.003 (2)
N3	0.027 (3)	0.047 (3)	0.014 (3)	0.001 (2)	−0.007 (2)	−0.001 (2)
C1	0.013 (3)	0.031 (3)	0.017 (3)	0.000 (2)	−0.009 (2)	0.002 (2)
C2	0.026 (3)	0.022 (3)	0.026 (4)	−0.006 (2)	−0.004 (3)	−0.004 (2)
C3	0.024 (3)	0.018 (3)	0.022 (3)	0.003 (2)	−0.006 (3)	0.000 (2)
C4	0.014 (3)	0.027 (3)	0.008 (3)	0.005 (2)	−0.001 (2)	0.002 (2)
C5	0.017 (3)	0.024 (3)	0.013 (3)	−0.004 (2)	−0.002 (2)	−0.001 (2)
C6	0.020 (3)	0.022 (3)	0.013 (3)	0.003 (2)	0.001 (2)	0.004 (2)
C7	0.017 (3)	0.021 (3)	0.018 (3)	0.000 (2)	−0.002 (2)	0.001 (2)
C8	0.010 (2)	0.023 (3)	0.010 (3)	0.0043 (19)	−0.002 (2)	0.000 (2)
C9	0.012 (3)	0.020 (3)	0.023 (3)	0.000 (2)	−0.004 (2)	0.001 (2)
C10	0.016 (2)	0.017 (2)	0.011 (3)	0.005 (2)	0.001 (2)	0.001 (2)
C11	0.012 (2)	0.021 (3)	0.010 (3)	0.002 (2)	−0.001 (2)	0.000 (2)
C12	0.017 (3)	0.020 (3)	0.010 (3)	−0.001 (2)	−0.001 (2)	−0.001 (2)
C13	0.022 (3)	0.017 (2)	0.013 (3)	0.005 (2)	0.000 (2)	0.001 (2)
C14	0.015 (3)	0.027 (3)	0.021 (3)	0.000 (2)	−0.006 (2)	−0.003 (2)
C15	0.012 (3)	0.021 (3)	0.018 (3)	0.000 (2)	−0.002 (2)	0.003 (2)

Geometric parameters (Å, º) top

Hg1—N1	2.392 (4)	C4—C5	1.384 (7)
Hg1—S1	2.4170 (13)	C4—C6	1.438 (7)
Hg1—S2ⁱ	2.4325 (13)	C5—H5	0.9500
Hg1—N2	2.568 (5)	C6—C7	1.178 (7)
S1—C14	1.682 (6)	C7—C8	1.448 (7)
S2—C15	1.671 (6)	C8—C9	1.392 (7)
N1—C1	1.338 (6)	C8—C13	1.402 (7)
N1—C5	1.351 (6)	C9—C10	1.381 (7)
N2—C15	1.151 (7)	C9—H9	0.9500
N3—C14	1.163 (8)	C10—C11	1.404 (7)
C1—C2	1.378 (7)	C10—H10	0.9500
C1—H1	0.9500	C11—C12	1.398 (7)
C2—C3	1.375 (7)	C11—C11ⁱⁱ	1.500 (9)
C2—H2	0.9500	C12—C13	1.371 (7)
C3—C4	1.413 (7)	C12—H12	0.9500
C3—H3	0.9500	C13—H13	0.9500

N1—Hg1—S1	109.28 (10)	N1—C5—H5	118.2
N1—Hg1—S2ⁱ	99.19 (10)	C4—C5—H5	118.2
S1—Hg1—S2ⁱ	148.61 (5)	C7—C6—C4	175.0 (6)
N1—Hg1—N2	84.04 (13)	C6—C7—C8	179.4 (6)
S1—Hg1—N2	98.29 (10)	C9—C8—C13	118.6 (4)
S2ⁱ—Hg1—N2	97.50 (11)	C9—C8—C7	120.5 (4)
C14—S1—Hg1	101.81 (19)	C13—C8—C7	120.9 (4)
C15—S2—Hg1ⁱⁱⁱ	99.43 (18)	C10—C9—C8	120.7 (5)
C1—N1—C5	117.6 (4)	C10—C9—H9	119.6
C1—N1—Hg1	119.6 (3)	C8—C9—H9	119.6
C5—N1—Hg1	122.7 (3)	C9—C10—C11	121.2 (5)
C15—N2—Hg1	146.1 (4)	C9—C10—H10	119.4
N1—C1—C2	123.2 (5)	C11—C10—H10	119.4
N1—C1—H1	118.4	C12—C11—C10	117.1 (4)
C2—C1—H1	118.4	C12—C11—C11ⁱⁱ	121.9 (6)
C3—C2—C1	119.2 (5)	C10—C11—C11ⁱⁱ	121.0 (6)
C3—C2—H2	120.4	C13—C12—C11	122.1 (5)
C1—C2—H2	120.4	C13—C12—H12	118.9
C2—C3—C4	119.2 (5)	C11—C12—H12	118.9
C2—C3—H3	120.4	C12—C13—C8	120.2 (5)
C4—C3—H3	120.4	C12—C13—H13	119.9
C5—C4—C3	117.3 (5)	C8—C13—H13	119.9
C5—C4—C6	121.7 (5)	N3—C14—S1	177.1 (5)
C3—C4—C6	121.0 (5)	N2—C15—S2	176.1 (5)
N1—C5—C4	123.6 (5)

C5—N1—C1—C2	0.2 (8)	C13—C8—C9—C10	−0.3 (8)
Hg1—N1—C1—C2	176.3 (4)	C7—C8—C9—C10	179.2 (5)
N1—C1—C2—C3	−0.6 (9)	C8—C9—C10—C11	1.7 (8)
C1—C2—C3—C4	0.1 (9)	C9—C10—C11—C12	−1.4 (8)
C2—C3—C4—C5	0.8 (8)	C9—C10—C11—C11ⁱⁱ	179.1 (6)
C2—C3—C4—C6	−177.2 (5)	C10—C11—C12—C13	−0.4 (8)
C1—N1—C5—C4	0.8 (8)	C11ⁱⁱ—C11—C12—C13	179.1 (6)
Hg1—N1—C5—C4	−175.2 (4)	C11—C12—C13—C8	1.8 (8)
C3—C4—C5—N1	−1.3 (8)	C9—C8—C13—C12	−1.5 (8)
C6—C4—C5—N1	176.8 (5)	C7—C8—C13—C12	179.1 (5)

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

Acknowledgements

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

References

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