Crystal structure of a zigzag CoII coordination polymer: catena-poly[[di­chlorido­bis­(methanol-κO)cobalt(II)]-μ-bis­(pyridin-3-ylmeth­yl)sulfane-κ2N:N′]

Moon, S.-H.; Seo, J.; Park, K.-M.

doi:10.1107/S2056989017016449

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Volume 73| Part 12| December 2017| Pages 1882-1884

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Crystal structure of a zigzag Co^II coordination polymer: catena-poly[[dichloridobis(methanol-κO)cobalt(II)]-μ-bis(pyridin-3-ylmethyl)sulfane-κ²N:N′]

Suk-Hee Moon,^a Joobeom Seo ^b ^* and Ki-Min Park ^c ^*

^aDepartment of Food and Nutrition, Kyungnam College of Information and Technology, Busan 47011, Republic of Korea, ^bMineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon 34132, Republic of Korea, and ^cResearch institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea
^*Correspondence e-mail: joobeomi@kigam.re.kr, kmpark@gnu.ac.kr

Edited by G. Smith, Queensland University of Technology, Australia (Received 28 October 2017; accepted 15 November 2017; online 17 November 2017)

Reaction of bis(pyridin-3-ylmethyl)sulfane (L) with cobalt(II) chloride in methanol led to the formation of the title coordination polymer, [CoCl₂(C₁₂H₁₂N₂S)(CH₃OH)₂]_n, in which the Co^II cation lies on a crystallographic inversion centre and the S atom of the L ligand lies on a twofold rotation axis. Each Co^II ion is coordinated by two pyridine N atoms from two bridging L ligands, two O atoms from methanol molecules and two chloride anions, all inversion-related. The complex unit has an elongated octahedral geometry, in which N₂O₂ donor atoms occupy the equatorial positions and two chloride anions occupy the axial positions. Each L ligand links two Co^II ions, forming an infinite zigzag chain propagating along the c-axis direction and further stabilized by O—H⋯Cl hydrogen bonds between the methanol molecules and the chloride anions. Adjacent chains in the structure are connected by intermolecular C—H⋯Cl hydrogen bonds, resulting in the formation of a three-dimensional supramolecular architecture.

Keywords: crystal structure; cobalt(II); dipyridyl ligand; chloride anion; zigzag chain; hydrogen bonding.

CCDC reference: 1585746

1. Chemical context

Up to now, large numbers of metal–organic coordination polymers with intriguing topologies and attractive properties have been constructed in which dipyridyl-type molecules functioning as bridging ligands have mainly been used (Leong & Vittal, 2011 ; Wang et al., 2012 ; Liu et al., 2011 ). Our group has also investigated several metal–organic coordination polymers with interesting topologies using such dipyridyl-type ligands (Moon et al., 2011 , 2016 , 2017 ; Lee et al., 2015 ; Ju et al., 2014 ; Im et al., 2017 ). In an extension of our research in this area, the title compound was prepared by the reaction of cobalt(II) chloride with bis(pyridin-3-ylmethyl)sulfane, C₁₂H₁₂N₂S, (L) as a flexible dipyridyl-type ligand [synthesized according to a literature procedure (Park et al., 2010 ; Lee et al., 2012 )]. Our group has previously reported the crystal structure of a looped-chain Co^II coordination polymer obtained through the reaction of cobalt(II) nitrate with L (Moon et al., 2017). In this article, we describe the crystal structure of the title compound, [Co(L)(CH₃OH)₂Cl₂]_n, with L = (pyridin-3-ylmethyl)sulfane, which adopts a one-dimensional zigzag topology.

2. Structural commentary

As shown in Figs. 1 and 2, the molecular structure of the title compound is generated by the combination of inversion and twofold rotation symmetries. Each Co^II cation lies on a crystallographic inversion centre, and the twofold rotation axis passes through the S atom of the L ligand. Therefore, the asymmetric unit comprises one half of a Co^II cation, one half of an L ligand, one chloride anion and one methanol molecule. The coordination geometry of the Co^II ion is elongated octahedral with the four equatorial positions being occupied by two pyridine N atoms from the two symmetry-related L ligands and two O atoms from two symmetry-related methanol molecules, and the two axial positions being occupied by two chlorido ligands (Fig. 1). Selected bond lengths and angles around the Co1 atom are listed in Table 1. The coordination geometry of the title compound is similar to that found in dichlorobis(methanol-κO)bis[N-(1-naphthyl)-N′-(3-pyridyl)urea-κN]cobalt(II) (Huang et al., 2008 ).

Table 1
Selected geometric parameters (Å, °)

Co1—O1	2.119 (2)	Co1—Cl1	2.4571 (11)
Co1—N1	2.153 (3)

O1—Co1—N1	88.20 (11)	N1—Co1—Cl1	92.11 (9)
O1—Co1—Cl1	90.53 (8)

Figure 1
A view of molecular structure of the title compound, showing the geometry around the Co^II centre and the atom-numbering scheme [symmetry codes: (iii) −x + 1, −y, −z; (iv) −x + 1, y, −z − $[{1\over 2}]$ ]. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

Figure 2
The zigzag chain structure of the title compound extending along the c axis. Yellow dashed lines represent intramolecular O—H⋯Cl hydrogen bonds in the zigzag chain. H atoms not involved in intermolecular interactions have been omitted for clarity.

Each L ligand bridges two Co^II ions into an infinite zigzag chain propagating along the c-axis direction (Fig. 2). The separation between the Co^II ions through a L ligand in the chain is 6.0595 (11) Å. The flexible thioether segment [C5—C6—S1—C6^iv—C5^iv; symmetry code: (iv) −x + 1, y, −z − $[{1\over 2}]$ ] of the L ligand shows a bent arrangement induced by a gauche–gauche configuration with a torsion angle of 74.4 (3)° for the C5—C6—S1—C6^iv and C6—S1—C6^iv—C5^iv units. This conformation of the L ligand is similar to those in a cyclic dimer-type silver(I) BF₄ complex, [Ag(L)]₂·2BF₄ (Seo et al., 2003 ), and a staircase-type copper(I) iodide coordination polymer, [(CuI)₂(L)]_n (Hanton et al., 2006 ). The zigzag topology of the chain may be induced by this conformation of the L ligand.

3. Supramolecular features

An O1—H⋯Cl1ⁱ hydrogen bond (Table 2; yellow dashed lines in Fig. 2; symmetry code: (i) −x + 1, y, −z + $[{1\over 2}]$ ) between the methanol molecule and the chloride anion contributes to the stabilization of the zigzag chain. In the crystal, weak C6—H⋯Cl1ⁱⁱ hydrogen bonds (Table 2; sky-blue dashed lines in Fig. 3) connect neighboring zigzag chains to generate a three-dimensional supramolecular network.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl1ⁱ	0.82	2.28	3.030 (3)	152
C6—H6A⋯Cl1ⁱⁱ	0.97	2.76	3.653 (4)	153
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y-{\script{1\over 2}}, -z]$ .

Figure 3
The three-dimensional supramolecular network formed through intermolecular C—H⋯Cl hydrogen bonds (sky-blue dashed lines) between the chains. H atoms not involved in intermolecular interactions have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, update May 2017; Groom et al., 2016 ) for the title ligand (L) gave three hits. Two of these (REJCAL, RENHOI; Hanton et al., 2006) are copper(I) iodide coordination polymers adopting staircase- and loop-type structures, respectively. The third (EXEZOW; Seo et al., 2003) is a silver(I) BF₄ complex with a cyclic dimer structure.

5. Synthesis and crystallization

The L ligand was synthesized according to a literature method (Park et al., 2010; Lee et al., 2012). Crystals of the title compound were obtained by slow evaporation of a methanol solution of the L ligand with CoCl₂·6H₂O in an 1:1 molar ratio.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically with C—H = 0.93 Å for Csp²—H, 0.96 Å for methyl C—H, 0.97 Å for methylene C—H, and 0.82 Å for alcohol O—H, and were refined as riding with U_iso(H) = 1.2U_eq(C,O).

Table 3
Experimental details

Crystal data
Chemical formula	[CoCl₂(C₁₂H₁₂N₂S)(CH₄O)₂]
M_r	410.21
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	11.419 (2), 13.363 (2), 12.119 (2)
β (°)	106.226 (4)
V (Å³)	1775.6 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.39
Crystal size (mm)	0.35 × 0.08 × 0.08

Data collection
Diffractometer	Bruker CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.627, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	5461, 1947, 1013
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.095, 0.92
No. of reflections	1947
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1585746

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989017016449/zs2393sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016449/zs2393Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

catena-Poly[[dichloridobis(methanol-κO)cobalt(II)]-µ-bis(pyridin-3-ylmethyl)sulfane-κ²N:N'] top

Crystal data top

[CoCl₂(C₁₂H₁₂N₂S)(CH₄O)₂]	F(000) = 844
M_r = 410.21	D_x = 1.534 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.419 (2) Å	Cell parameters from 5771 reflections
b = 13.363 (2) Å	θ = 2.4–28.2°
c = 12.119 (2) Å	µ = 1.39 mm⁻¹
β = 106.226 (4)°	T = 298 K
V = 1775.6 (6) Å³	Needle, violet
Z = 4	0.35 × 0.08 × 0.08 mm

Data collection top

Bruker CCD area detector diffractometer	1013 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.098
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 27.0°, θ_min = 2.4°
T_min = 0.627, T_max = 0.888	h = −14→14
5461 measured reflections	k = −17→13
1947 independent reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0319P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
1947 reflections	Δρ_max = 0.37 e Å⁻³
102 parameters	Δρ_min = −0.32 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.

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

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.0000	0.0000	0.0333 (2)
Cl1	0.64563 (9)	0.04038 (8)	0.18588 (8)	0.0414 (3)
S1	0.5000	−0.44202 (11)	−0.2500	0.0611 (5)
O1	0.3665 (2)	−0.0394 (2)	0.0836 (2)	0.0467 (8)
H1A	0.3528	−0.0010	0.1313	0.056*
N1	0.5559 (3)	−0.1544 (2)	0.0120 (3)	0.0361 (8)
C1	0.5742 (3)	−0.2051 (3)	−0.0774 (3)	0.0365 (10)
H1	0.5682	−0.1696	−0.1448	0.044*
C2	0.5680 (4)	−0.2068 (3)	0.1089 (4)	0.0467 (12)
H2	0.5578	−0.1734	0.1729	0.056*
C3	0.5946 (4)	−0.3071 (4)	0.1189 (4)	0.0599 (14)
H3	0.6021	−0.3408	0.1877	0.072*
C4	0.6099 (4)	−0.3567 (3)	0.0235 (4)	0.0562 (13)
H4	0.6262	−0.4250	0.0274	0.067*
C5	0.6011 (4)	−0.3051 (3)	−0.0771 (4)	0.0416 (11)
C6	0.6204 (4)	−0.3550 (3)	−0.1819 (4)	0.0543 (13)
H6A	0.6975	−0.3907	−0.1601	0.065*
H6B	0.6260	−0.3040	−0.2372	0.065*
C7	0.2751 (4)	−0.1150 (3)	0.0567 (4)	0.0570 (13)
H7A	0.2241	−0.1053	−0.0202	0.068*
H7B	0.2265	−0.1112	0.1096	0.068*
H7C	0.3132	−0.1796	0.0625	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0461 (5)	0.0281 (5)	0.0281 (4)	0.0030 (4)	0.0143 (4)	0.0000 (4)
Cl1	0.0512 (7)	0.0429 (6)	0.0305 (6)	0.0051 (5)	0.0122 (5)	0.0002 (4)
S1	0.0791 (14)	0.0273 (10)	0.0658 (13)	0.000	0.0021 (11)	0.000
O1	0.064 (2)	0.0387 (17)	0.0454 (18)	−0.0111 (15)	0.0286 (17)	−0.0149 (13)
N1	0.048 (2)	0.029 (2)	0.034 (2)	0.0012 (16)	0.0140 (18)	0.0029 (16)
C1	0.039 (3)	0.035 (3)	0.035 (2)	0.004 (2)	0.010 (2)	0.000 (2)
C2	0.061 (3)	0.041 (3)	0.039 (3)	0.006 (2)	0.016 (2)	0.002 (2)
C3	0.080 (4)	0.047 (3)	0.050 (3)	0.005 (3)	0.013 (3)	0.020 (3)
C4	0.072 (4)	0.025 (3)	0.067 (4)	0.010 (2)	0.012 (3)	0.010 (2)
C5	0.034 (3)	0.033 (3)	0.056 (3)	0.006 (2)	0.011 (2)	−0.003 (2)
C6	0.052 (3)	0.045 (3)	0.064 (3)	0.015 (2)	0.015 (3)	−0.014 (2)
C7	0.068 (3)	0.054 (3)	0.052 (3)	−0.013 (3)	0.022 (3)	−0.008 (2)

Geometric parameters (Å, º) top

Co1—O1	2.119 (2)	C1—H1	0.9300
Co1—O1ⁱ	2.119 (2)	C2—C3	1.372 (6)
Co1—N1	2.153 (3)	C2—H2	0.9300
Co1—N1ⁱ	2.153 (3)	C3—C4	1.385 (6)
Co1—Cl1ⁱ	2.4571 (11)	C3—H3	0.9300
Co1—Cl1	2.4571 (11)	C4—C5	1.380 (6)
S1—C6	1.814 (4)	C4—H4	0.9300
S1—C6ⁱⁱ	1.814 (4)	C5—C6	1.504 (5)
O1—C7	1.424 (4)	C6—H6A	0.9700
O1—H1A	0.8200	C6—H6B	0.9700
N1—C2	1.342 (5)	C7—H7A	0.9600
N1—C1	1.343 (5)	C7—H7B	0.9600
C1—C5	1.371 (5)	C7—H7C	0.9600

O1—Co1—O1ⁱ	180.0	N1—C2—C3	123.6 (4)
O1—Co1—N1	88.20 (11)	N1—C2—H2	118.2
O1ⁱ—Co1—N1	91.80 (11)	C3—C2—H2	118.2
O1—Co1—N1ⁱ	91.80 (11)	C2—C3—C4	118.0 (4)
O1ⁱ—Co1—N1ⁱ	88.20 (11)	C2—C3—H3	121.0
N1—Co1—N1ⁱ	180.0	C4—C3—H3	121.0
O1—Co1—Cl1ⁱ	89.47 (8)	C5—C4—C3	120.3 (4)
O1ⁱ—Co1—Cl1ⁱ	90.53 (8)	C5—C4—H4	119.9
N1—Co1—Cl1ⁱ	87.89 (9)	C3—C4—H4	119.9
N1ⁱ—Co1—Cl1ⁱ	92.11 (9)	C1—C5—C4	116.7 (4)
O1—Co1—Cl1	90.53 (8)	C1—C5—C6	121.0 (4)
O1ⁱ—Co1—Cl1	89.47 (8)	C4—C5—C6	122.2 (4)
N1—Co1—Cl1	92.11 (9)	C5—C6—S1	113.4 (3)
N1ⁱ—Co1—Cl1	87.89 (9)	C5—C6—H6A	108.9
Cl1ⁱ—Co1—Cl1	180.0	S1—C6—H6A	108.9
C6—S1—C6ⁱⁱ	100.3 (3)	C5—C6—H6B	108.9
C7—O1—Co1	130.2 (2)	S1—C6—H6B	108.9
C7—O1—H1A	109.5	H6A—C6—H6B	107.7
Co1—O1—H1A	119.1	O1—C7—H7A	109.5
C2—N1—C1	116.2 (4)	O1—C7—H7B	109.5
C2—N1—Co1	121.1 (3)	H7A—C7—H7B	109.5
C1—N1—Co1	122.6 (3)	O1—C7—H7C	109.5
N1—C1—C5	125.1 (4)	H7A—C7—H7C	109.5
N1—C1—H1	117.5	H7B—C7—H7C	109.5
C5—C1—H1	117.5

C2—N1—C1—C5	1.6 (6)	N1—C1—C5—C6	−179.8 (4)
Co1—N1—C1—C5	−175.0 (3)	C3—C4—C5—C1	−1.4 (7)
C1—N1—C2—C3	−1.6 (6)	C3—C4—C5—C6	178.3 (4)
Co1—N1—C2—C3	175.1 (3)	C1—C5—C6—S1	−110.7 (4)
N1—C2—C3—C4	0.1 (7)	C4—C5—C6—S1	69.6 (5)
C2—C3—C4—C5	1.4 (7)	C6ⁱⁱ—S1—C6—C5	74.4 (3)
N1—C1—C5—C4	−0.1 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1ⁱⁱⁱ	0.82	2.28	3.030 (3)	152
C6—H6A···Cl1^iv	0.97	2.76	3.653 (4)	153

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

Funding information

This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2015R1D1A3A01020410).

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