A two-dimensional copper(I) coordination polymer based on 1-[2-(cyclo­hexyl­sulfan­yl)eth­yl]pyridin-2(1H)-one

Park, H.; Kim, J.; Im, H.; Kim, T.H.

doi:10.1107/S2056989017015377

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ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1782-1785

https://doi.org/10.1107/S2056989017015377

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A two-dimensional copper(I) coordination polymer based on 1-[2-(cyclohexylsulfanyl)ethyl]pyridin-2(1H)-one

Hyunjin Park,^a Jineun Kim,^a ^* Hansu Im ^a and Tae Ho Kim ^a ^*

^aDepartment of Chemistry (BK21 plus) and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 52828, Republic of Korea
^*Correspondence e-mail: thkim@gnu.ac.kr, jekim@gnu.ac.kr

Edited by J. Simpson, University of Otago, New Zealand (Received 16 October 2017; accepted 23 October 2017; online 27 October 2017)

The reaction of copper(I) iodide with 1-[2-(cyclohexylsulfanyl)ethyl]pyridin-2(1H)-one (L, C₁₃H₁₉NOS) in acetonitrile/dichloromethane results in a crystalline coordination polymer, namely poly[bis{μ₂-1-[2-(cyclohexylsulfanyl)ethyl]pyridin-2(1H)-one}tetra-μ₃-iodidotetracopper(I)], [Cu₄I₄L₂]_n. The asymmetric unit comprises two ligand molecules, four copper(I) ions and four iodide ions. Interestingly, the O atoms are bound to the soft copper(I) ions. The stair-step clusters of Cu and I atoms in the asymmetric unit are linked repeatedly, giving rise to infinite chains along [100]. Neighbouring infinite chains are linked through the L molecules, forming a two-dimensional brick-wall structure. These two-dimensional networks are stacked alternately along [001]. Additionally, there are intermolecular C—H⋯I hydrogen bonds and C—H⋯π interactions between the ligands.

Keywords: crystal structure; coordination polymer; copper(I) iodide; S/O donors.

CCDC reference: 1581394

1. Chemical context

Copper(I) complexes have been studied continuously over several decades because of their potential applications as sensors, catalysts, and gas storage materials (Lin et al., 2016 ; Ananthnag et al., 2015 ; Pal et al., 2015 ). They exhibit a variety of structures, photoluminescence, and other physical properties as a result of the d¹⁰ electron configuration of Cu^I (Peng et al., 2010 ; Ford et al., 1999 ; Kobayashi & Kato, 2017 ). In addition, the arrangement of donor atoms in the ligands may affect both the structures of the complexes and their physical properties. Copper(I) complexes of flexible ligands with N/S donor atoms have been studied (Jeon et al., 2014 ; Cho et al., 2015 ). Mechanochromism, vapochromism and solvatochromism of such complexes have also been reported (Kwon et al., 2017 ; Kang et al., 2015 ; Kim et al., 2013 ). Herein we describe the synthesis and crystal structure of a copper(I) complex [Cu₄I₄L₂]_n of L (C₁₃H₁₉NOS) with O/S donor atoms. Cu^I—O bonds have been reported previously in copper(I) coordination polymers with phosphine ligands (Darensbourg et al., 1998 ) but those with an O/S donor ligand set are unique as far as we know.

2. Structural commentary

The asymmetric unit of the title compound, [Cu₄I₄L₂]_n, comprises four copper(I) ions, four μ₃-iodide ions, and two L ligands as shown in Fig. 1. In L^A (identified by S1) and L^B (identified by S2), the pyridyl and cyclohexyl rings are in anti and gauche conformations with torsion angles of −154.7 (6)° [C6—S1—C7—C8] and 62.3 (7)° [C19—S2—C20—C21], respectively. All of the Cu^I atoms (Cu1–Cu4) have distorted tetrahedral coordination geometries. The Cu1 and Cu2 atoms are bound by three μ₃-iodide anions and one S atom, while Cu3 and Cu4 are coordinated by three μ₃-iodide ions and one O atom. The ranges of interatomic distances in the title compound are 2.7082 (15)–2.7444 (14) Å, 2.297 (2)–2.314 (2) Å, 2.6210 (12)–2.7230 (12) Å, and 2.071 (6)–2.087 (6) Å for Cu—Cu, Cu—S, Cu—I, and Cu—O, respectively (Table 1). Interestingly, the O atoms bind to the soft copper(I) cations, implying that the carbonyl O atoms conjugated with pyridyl rings are softer than the hard, ether-like O atoms.

Table 1
Selected bond lengths (Å)

Cu1—S1	2.314 (2)	Cu2—I1	2.7230 (12)
Cu1—I1	2.6467 (12)	Cu3—O1ⁱ	2.087 (6)
Cu1—I2	2.6669 (12)	Cu3—I3	2.6210 (12)
Cu1—I3	2.6939 (12)	Cu3—I1	2.6458 (12)
Cu1—Cu3	2.7444 (14)	Cu3—I4ⁱⁱ	2.6833 (12)
Cu2—S2	2.297 (2)	Cu4—O2ⁱⁱⁱ	2.071 (6)
Cu2—I4	2.6256 (12)	Cu4—I4	2.6412 (13)
Cu2—I2	2.6544 (12)	Cu4—I3^iv	2.6800 (13)
Cu2—Cu4	2.7082 (15)	Cu4—I2	2.7084 (13)
Symmetry codes: (i) x, y+1, z; (ii) x-1, y, z; (iii) x, y-1, z; (iv) x+1, y, z.

Figure 1
The molecular structure of the title compound, with the atom labelling and displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

3. Supramolecular features

The step-like clusters of Cu and I atoms in the asymmetric unit are linked repeatedly, generating infinite chains along [100]. Neighbouring infinite chains are linked by the L molecules, forming a two-dimensional brick-wall structure parallel to (001) as shown in Fig. 2 (Tzeng & Chang, 2009 ). Yellow dashed lines display intermolecular C8—H8A⋯I4ⁱⁱ, C12—H12⋯I1ⁱⁱⁱ and C21—H21B⋯I3^iv [H⋯I = 3.26, 3.30, and 3.08 Å, respectively] hydrogen bonds between ligands. Red dashed lines display intermolecular C5—H5A⋯Cg1^v [H⋯Cg1=3.00 Å] interactions between the ligands (Fig. 2 and Table 2). The two-dimensional brick-wall networks are stacked in an ⋯ababab⋯ fashion along [001] (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N2/C22–C26 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯I4ⁱⁱ	0.99	3.26	4.107 (8)	145
C12—H12⋯I1ⁱⁱⁱ	0.95	3.30	3.899 (8)	123
C21—H21B⋯I3^iv	0.99	3.08	3.923 (8)	144
C5—H5A⋯Cg1^v	0.99	3.00	3.948 (9)	162
Symmetry codes: (ii) x-1, y, z; (iii) x, y-1, z; (iv) x+1, y, z; (v) x-1, y-1, z.

Figure 2
A packing diagram showing the intermolecular C—H⋯I hydrogen bonds (yellow dashed lines) and C—H⋯π interactions (red dashed lines) between ligands. H atoms have been omitted for clarity.

Figure 3
The two-dimensional brick-wall networks are stacked in an ⋯ababab⋯ fashion along [001]. All H atoms have been omitted for clarity.

4. Database survey

Syntheses and properties of the copper(I) complexes of N/S mixed donor atom ligands have been reported (Jeon et al., 2014; Cho et al., 2015). Copper(I) complexes of N/S mixed-donor atom ligands with cyclohexyl group have also been reported (Park et al., 2016 , 2017 ). In addition, a database search (CSD Version 5.27, last update February 2017; Groom et al., 2016 ) showed the crystal structures of three complexes with infinite stair-step (CuI)_n cluster units (Jess et al., 2007 ; Jess & Näther, 2004 ; Graham et al., 2000 ).

5. Synthesis and crystallization

Synthesis of 1-[2-(cyclohexylsulfanyl)ethyl]pyridin-2(1H)-one (L)

Thionyl chloride (2.38 g, 20.0 mmol) was added dropwise to 2-(cyclohexylthio)ethanol (3.21 g, 20 mmol) in chloroform. The mixture was stirred under reflux for 1 h then cooled to 253 K. Chloroform was removed, yielding crude 2-chloroethylcyclohexylsulfide. 2-Hydroxypyridine (1.90 g, 20 mmol) and potassium hydroxide (1.12 g, 20 mmol) were dissolved in 10 ml of tetrahydrofuran and 5 ml of water, and then the solution was added dropwise to the crude chloride. The solution was refluxed for 24 h and cooled. The crude product was extracted by dichloromethane. The dichloromethane layer was dried with anhydrous Na₂SO₄, and evaporated to give a crude oil. Column chromatography (silica gel, MeCOOEt/n–C₆H₁₄ = 30/70 (v/v), R_f = 0.28) (Park et al., 2016). ¹H NMR (300 MHz, CDCl₃): 7.28 (dd, 2H, py), 6.52 (d, H, py), 6.11 (d, H, py), 4.01 (t, 2H, NCH₂), 2.85 (t, 2H, CH₂S), 2.51 (d, H, SCH), 2.00–1.13 [m, 10H, (CH₂)₅]; ¹³C NMR (39.51 MHz, DMSO): 161.33, 140.03, 139.52, 119.40, 104.86, 49.21, 42.48, 33.15 27.71, 25.44, 25.29.

Preparation of [Cu₄I₄L₂]_n

A dichloromethane (5 ml) solution of L (0.006 g, 0.025 mmol) was allowed to mix with an acetonitrile (5 ml) solution of CuI (0.010 g, 0.053 mmol). The colourless precipitate was filtered and washed with a diethyl ether/acetonitrile (5/1 v/v) solution. Single crystals suitable for X-ray analysis were obtained by slow evaporation of dichloromethane from the reaction mixture.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic C—H groups, C—H = 0.99 Å and U_iso(H) = 1.2U_eq(C) for CH₂ groups, and C—H = 1.00 Å and U_iso(H) = 1.2U_eq(C) for Csp³—H groups.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₄I₄(C₁₃H₁₉NOS)₂]
M_r	1236.46
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	173
a, b, c (Å)	8.5922 (3), 9.1285 (3), 21.5629 (6)
β (°)	96.754 (1)
V (Å³)	1679.53 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	6.33
Crystal size (mm)	0.35 × 0.27 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.402, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	29149, 7588, 7376
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.072, 1.10
No. of reflections	7588
No. of parameters	362
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.35, −0.84
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	0.07 (3)
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: 1581394

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989017015377/sj5538sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015377/sj5538Isup2.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).

Poly[bis{µ₂-1-[2-(cyclohexylsulfanyl)ethyl]pyridin-2(1H)-one}tetra-µ₃-iodidotetracopper(I)] top

Crystal data top

[Cu₄I₄(C₁₃H₁₉NOS)₂]	F(000) = 1168
M_r = 1236.46	D_x = 2.445 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 8.5922 (3) Å	Cell parameters from 9858 reflections
b = 9.1285 (3) Å	θ = 2.4–27.5°
c = 21.5629 (6) Å	µ = 6.33 mm⁻¹
β = 96.754 (1)°	T = 173 K
V = 1679.53 (9) Å³	Plate, colourless
Z = 2	0.35 × 0.27 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	7376 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.047
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 27.5°, θ_min = 1.0°
T_min = 0.402, T_max = 0.746	h = −11→10
29149 measured reflections	k = −11→11
7588 independent reflections	l = −27→27

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0224P)² + 3.3344P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.072	(Δ/σ)_max = 0.001
S = 1.10	Δρ_max = 2.35 e Å⁻³
7588 reflections	Δρ_min = −0.84 e Å⁻³
362 parameters	Absolute structure: Refined as an inversion twin.
1 restraint	Absolute structure parameter: 0.07 (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. Refined as a 2-component inversion twin

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

	x	y	z	U_iso*/U_eq
Cu1	0.14206 (13)	0.42954 (11)	0.71506 (5)	0.0218 (2)
Cu2	0.46250 (13)	0.57157 (12)	0.77959 (5)	0.0208 (2)
Cu3	−0.03849 (13)	0.58815 (13)	0.78775 (5)	0.0243 (2)
Cu4	0.66577 (14)	0.42199 (11)	0.71635 (5)	0.0259 (3)
I1	0.22291 (6)	0.45860 (6)	0.83671 (2)	0.01699 (11)
I2	0.38662 (6)	0.51673 (8)	0.65893 (3)	0.01980 (13)
I3	−0.11520 (6)	0.57738 (7)	0.66655 (2)	0.01633 (12)
I4	0.72270 (6)	0.46385 (6)	0.83810 (2)	0.01796 (12)
S1	0.0444 (2)	0.1958 (2)	0.69520 (9)	0.0164 (4)
S2	0.4169 (2)	0.8155 (2)	0.79653 (9)	0.0148 (4)
O1	−0.0391 (7)	−0.1909 (6)	0.8126 (3)	0.0204 (13)
O2	0.6473 (7)	1.1978 (6)	0.7028 (3)	0.0186 (13)
N1	0.0334 (8)	0.0164 (9)	0.8668 (3)	0.0157 (14)
N2	0.6273 (7)	0.9801 (8)	0.6501 (3)	0.0148 (14)
C1	0.1061 (10)	0.2002 (9)	0.5753 (4)	0.0179 (17)
H1A	−0.0086	0.2068	0.5636	0.022*
H1B	0.1467	0.3007	0.5835	0.022*
C2	0.1812 (11)	0.1344 (10)	0.5219 (4)	0.0240 (19)
H2A	0.2965	0.1348	0.5323	0.029*
H2B	0.1551	0.1948	0.4840	0.029*
C3	0.1253 (11)	−0.0219 (10)	0.5087 (4)	0.0264 (19)
H3A	0.1808	−0.0644	0.4752	0.032*
H3B	0.0116	−0.0217	0.4941	0.032*
C4	0.1567 (11)	−0.1158 (10)	0.5679 (4)	0.0230 (19)
H4A	0.1128	−0.2151	0.5594	0.028*
H4B	0.2712	−0.1257	0.5794	0.028*
C5	0.0835 (10)	−0.0479 (9)	0.6222 (4)	0.0197 (17)
H5A	−0.0321	−0.0486	0.6126	0.024*
H5B	0.1115	−0.1074	0.6602	0.024*
C6	0.1398 (9)	0.1084 (8)	0.6341 (3)	0.0128 (15)
H6	0.2555	0.1072	0.6470	0.015*
C7	0.1085 (9)	0.0872 (10)	0.7639 (4)	0.0168 (15)
H7A	0.1198	−0.0167	0.7520	0.020*
H7B	0.2115	0.1227	0.7836	0.020*
C8	−0.0127 (10)	0.1007 (9)	0.8096 (4)	0.0178 (16)
H8A	−0.0249	0.2051	0.8205	0.021*
H8B	−0.1151	0.0648	0.7896	0.021*
C9	0.0908 (10)	0.0879 (10)	0.9203 (4)	0.0204 (17)
H9	0.1047	0.1911	0.9199	0.024*
C10	0.1273 (11)	0.0125 (11)	0.9735 (4)	0.026 (2)
H10	0.1665	0.0632	1.0106	0.031*
C11	0.1087 (11)	−0.1392 (10)	0.9752 (4)	0.026 (2)
H11	0.1344	−0.1920	1.0130	0.031*
C12	0.0525 (10)	−0.2107 (9)	0.9212 (4)	0.0213 (19)
H12	0.0394	−0.3140	0.9221	0.026*
C13	0.0133 (10)	−0.1352 (9)	0.8641 (4)	0.0171 (17)
C14	0.5272 (11)	0.8042 (9)	0.9183 (4)	0.0205 (18)
H14A	0.5473	0.6987	0.9122	0.025*
H14B	0.4164	0.8157	0.9258	0.025*
C15	0.6351 (11)	0.8607 (10)	0.9755 (4)	0.025 (2)
H15A	0.6108	0.8087	1.0135	0.030*
H15B	0.7458	0.8407	0.9699	0.030*
C16	0.6116 (12)	1.0253 (10)	0.9833 (4)	0.025 (2)
H16A	0.5038	1.0435	0.9934	0.030*
H16B	0.6855	1.0611	1.0188	0.030*
C17	0.6371 (11)	1.1094 (10)	0.9256 (4)	0.0240 (19)
H17A	0.7483	1.1007	0.9183	0.029*
H17B	0.6146	1.2143	0.9320	0.029*
C18	0.5324 (12)	1.0535 (9)	0.8678 (4)	0.023 (2)
H18A	0.4211	1.0728	0.8728	0.028*
H18B	0.5579	1.1067	0.8303	0.028*
C19	0.5564 (10)	0.8896 (9)	0.8591 (4)	0.0174 (17)
H19	0.6658	0.8711	0.8495	0.021*
C20	0.4537 (9)	0.9200 (9)	0.7285 (4)	0.0182 (17)
H20A	0.3767	0.8904	0.6930	0.022*
H20B	0.4361	1.0250	0.7368	0.022*
C21	0.6182 (9)	0.9018 (9)	0.7097 (4)	0.0150 (16)
H21A	0.6964	0.9424	0.7426	0.018*
H21B	0.6414	0.7966	0.7046	0.018*
C22	0.6172 (10)	0.9017 (10)	0.5954 (4)	0.0208 (18)
H22	0.6056	0.7983	0.5967	0.025*
C23	0.6234 (10)	0.9677 (11)	0.5402 (4)	0.0247 (19)
H23	0.6164	0.9119	0.5028	0.030*
C24	0.6405 (10)	1.1220 (10)	0.5384 (4)	0.024 (2)
H24	0.6450	1.1701	0.4996	0.029*
C25	0.6506 (10)	1.2014 (10)	0.5922 (4)	0.0204 (18)
H25	0.6641	1.3046	0.5905	0.024*
C26	0.6411 (9)	1.1320 (9)	0.6513 (4)	0.0161 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0283 (6)	0.0185 (5)	0.0189 (5)	0.0022 (4)	0.0032 (4)	−0.0009 (4)
Cu2	0.0242 (6)	0.0175 (5)	0.0204 (5)	0.0019 (5)	0.0022 (4)	0.0004 (4)
Cu3	0.0324 (6)	0.0188 (5)	0.0213 (6)	0.0011 (5)	0.0015 (5)	−0.0030 (5)
Cu4	0.0350 (7)	0.0201 (5)	0.0231 (6)	−0.0005 (5)	0.0051 (5)	−0.0035 (4)
I1	0.0184 (2)	0.0185 (2)	0.0138 (2)	−0.0043 (2)	0.00072 (19)	0.0002 (2)
I2	0.0172 (3)	0.0261 (2)	0.0159 (3)	−0.0023 (2)	0.0014 (2)	−0.0020 (2)
I3	0.0174 (3)	0.0159 (2)	0.0156 (2)	0.0027 (2)	0.0016 (2)	0.0016 (2)
I4	0.0189 (2)	0.0196 (2)	0.0154 (2)	0.0012 (2)	0.00160 (19)	0.0013 (2)
S1	0.0189 (10)	0.0158 (9)	0.0146 (10)	0.0038 (8)	0.0018 (8)	0.0016 (7)
S2	0.0158 (10)	0.0137 (8)	0.0148 (10)	0.0001 (7)	0.0010 (8)	0.0008 (7)
O1	0.032 (4)	0.014 (3)	0.014 (3)	−0.003 (2)	−0.003 (3)	−0.004 (2)
O2	0.019 (3)	0.016 (3)	0.021 (3)	−0.002 (2)	0.005 (2)	−0.001 (3)
N1	0.019 (3)	0.015 (3)	0.013 (3)	0.002 (3)	0.004 (3)	0.000 (3)
N2	0.011 (3)	0.017 (4)	0.016 (3)	0.000 (3)	0.000 (2)	−0.002 (3)
C1	0.023 (4)	0.017 (4)	0.012 (4)	0.001 (3)	−0.002 (3)	0.005 (3)
C2	0.024 (5)	0.028 (5)	0.020 (5)	−0.002 (4)	0.003 (4)	0.001 (4)
C3	0.033 (5)	0.026 (5)	0.019 (4)	0.001 (4)	0.001 (4)	−0.003 (4)
C4	0.030 (5)	0.018 (4)	0.020 (5)	0.001 (4)	−0.001 (4)	−0.005 (3)
C5	0.025 (4)	0.015 (4)	0.018 (4)	−0.005 (4)	−0.001 (3)	−0.001 (3)
C6	0.017 (4)	0.012 (4)	0.009 (4)	0.005 (3)	0.000 (3)	0.001 (3)
C7	0.016 (4)	0.019 (4)	0.016 (4)	0.005 (3)	0.002 (3)	0.002 (3)
C8	0.020 (4)	0.014 (4)	0.019 (4)	0.000 (3)	0.003 (3)	0.004 (3)
C9	0.026 (5)	0.021 (4)	0.016 (4)	−0.004 (4)	0.008 (3)	0.000 (4)
C10	0.032 (5)	0.034 (5)	0.011 (4)	−0.002 (5)	−0.002 (4)	−0.003 (4)
C11	0.030 (5)	0.031 (5)	0.018 (5)	0.011 (4)	0.004 (4)	0.008 (4)
C12	0.027 (5)	0.015 (4)	0.022 (5)	−0.001 (3)	0.005 (4)	0.002 (3)
C13	0.015 (4)	0.014 (4)	0.023 (5)	−0.001 (3)	0.006 (3)	0.002 (3)
C14	0.028 (5)	0.016 (4)	0.017 (4)	0.001 (3)	0.001 (4)	−0.002 (3)
C15	0.030 (5)	0.025 (4)	0.017 (5)	0.004 (4)	−0.006 (4)	0.003 (4)
C16	0.030 (5)	0.025 (4)	0.020 (5)	−0.009 (4)	0.001 (4)	−0.008 (4)
C17	0.030 (5)	0.024 (4)	0.016 (4)	0.000 (4)	−0.001 (4)	−0.002 (3)
C18	0.036 (6)	0.017 (5)	0.013 (4)	0.000 (3)	−0.006 (4)	0.002 (3)
C19	0.015 (4)	0.021 (4)	0.017 (4)	−0.004 (3)	0.005 (3)	−0.002 (3)
C20	0.018 (4)	0.018 (4)	0.019 (4)	−0.001 (3)	0.001 (3)	0.006 (3)
C21	0.015 (4)	0.016 (4)	0.013 (4)	0.000 (3)	−0.002 (3)	0.004 (3)
C22	0.019 (4)	0.021 (4)	0.022 (5)	−0.002 (4)	0.001 (4)	−0.006 (4)
C23	0.022 (4)	0.034 (5)	0.019 (4)	0.004 (4)	0.006 (3)	−0.004 (4)
C24	0.027 (5)	0.030 (5)	0.015 (4)	−0.010 (4)	0.003 (4)	0.005 (4)
C25	0.018 (4)	0.020 (4)	0.022 (5)	0.000 (3)	−0.001 (4)	0.006 (4)
C26	0.009 (4)	0.020 (4)	0.019 (4)	0.001 (3)	0.004 (3)	0.000 (3)

Geometric parameters (Å, º) top

Cu1—S1	2.314 (2)	C5—C6	1.519 (11)
Cu1—I1	2.6467 (12)	C5—H5A	0.9900
Cu1—I2	2.6669 (12)	C5—H5B	0.9900
Cu1—I3	2.6939 (12)	C6—H6	1.0000
Cu1—Cu3	2.7444 (14)	C7—C8	1.520 (10)
Cu2—S2	2.297 (2)	C7—H7A	0.9900
Cu2—I4	2.6256 (12)	C7—H7B	0.9900
Cu2—I2	2.6544 (12)	C8—H8A	0.9900
Cu2—Cu4	2.7082 (15)	C8—H8B	0.9900
Cu2—I1	2.7230 (12)	C9—C10	1.343 (12)
Cu3—O1ⁱ	2.087 (6)	C9—H9	0.9500
Cu3—I3	2.6210 (12)	C10—C11	1.395 (14)
Cu3—I1	2.6458 (12)	C10—H10	0.9500
Cu3—I4ⁱⁱ	2.6833 (12)	C11—C12	1.374 (13)
Cu4—O2ⁱⁱⁱ	2.071 (6)	C11—H11	0.9500
Cu4—I4	2.6412 (13)	C12—C13	1.415 (12)
Cu4—I3^iv	2.6800 (13)	C12—H12	0.9500
Cu4—I2	2.7084 (13)	C14—C19	1.541 (11)
I3—Cu4ⁱⁱ	2.6800 (13)	C14—C15	1.541 (12)
I4—Cu3^iv	2.6834 (12)	C14—H14A	0.9900
S1—C7	1.814 (8)	C14—H14B	0.9900
S1—C6	1.816 (8)	C15—C16	1.528 (13)
S2—C20	1.808 (8)	C15—H15A	0.9900
S2—C19	1.826 (9)	C15—H15B	0.9900
O1—C13	1.256 (10)	C16—C17	1.500 (12)
O1—Cu3ⁱⁱⁱ	2.087 (6)	C16—H16A	0.9900
O2—C26	1.259 (10)	C16—H16B	0.9900
O2—Cu4ⁱ	2.071 (6)	C17—C18	1.535 (12)
N1—C9	1.367 (11)	C17—H17A	0.9900
N1—C13	1.395 (11)	C17—H17B	0.9900
N1—C8	1.467 (10)	C18—C19	1.525 (11)
N2—C22	1.374 (11)	C18—H18A	0.9900
N2—C26	1.391 (11)	C18—H18B	0.9900
N2—C21	1.481 (10)	C19—H19	1.0000
C1—C2	1.509 (12)	C20—C21	1.525 (11)
C1—C6	1.520 (10)	C20—H20A	0.9900
C1—H1A	0.9900	C20—H20B	0.9900
C1—H1B	0.9900	C21—H21A	0.9900
C2—C3	1.522 (13)	C21—H21B	0.9900
C2—H2A	0.9900	C22—C23	1.341 (12)
C2—H2B	0.9900	C22—H22	0.9500
C3—C4	1.535 (12)	C23—C24	1.417 (15)
C3—H3A	0.9900	C23—H23	0.9500
C3—H3B	0.9900	C24—C25	1.362 (13)
C4—C5	1.524 (11)	C24—H24	0.9500
C4—H4A	0.9900	C25—C26	1.433 (12)
C4—H4B	0.9900	C25—H25	0.9500

S1—Cu1—I1	108.85 (6)	C5—C6—C1	110.5 (7)
S1—Cu1—I2	118.63 (7)	C5—C6—S1	112.0 (6)
I1—Cu1—I2	106.91 (4)	C1—C6—S1	107.7 (5)
S1—Cu1—I3	97.29 (7)	C5—C6—H6	108.8
I1—Cu1—I3	116.26 (4)	C1—C6—H6	108.8
I2—Cu1—I3	109.18 (4)	S1—C6—H6	108.8
S1—Cu1—Cu3	112.03 (7)	C8—C7—S1	108.7 (5)
I1—Cu1—Cu3	58.75 (3)	C8—C7—H7A	110.0
I2—Cu1—Cu3	129.07 (5)	S1—C7—H7A	110.0
I3—Cu1—Cu3	57.62 (3)	C8—C7—H7B	110.0
S2—Cu2—I4	115.97 (7)	S1—C7—H7B	110.0
S2—Cu2—I2	108.17 (7)	H7A—C7—H7B	108.3
I4—Cu2—I2	119.84 (4)	N1—C8—C7	111.4 (6)
S2—Cu2—Cu4	134.49 (7)	N1—C8—H8A	109.4
I4—Cu2—Cu4	59.34 (4)	C7—C8—H8A	109.4
I2—Cu2—Cu4	60.66 (4)	N1—C8—H8B	109.4
S2—Cu2—I1	98.23 (6)	C7—C8—H8B	109.4
I4—Cu2—I1	106.68 (4)	H8A—C8—H8B	108.0
I2—Cu2—I1	105.09 (4)	C10—C9—N1	120.1 (9)
Cu4—Cu2—I1	127.12 (5)	C10—C9—H9	119.9
O1ⁱ—Cu3—I3	106.53 (17)	N1—C9—H9	119.9
O1ⁱ—Cu3—I1	110.92 (18)	C9—C10—C11	121.0 (9)
I3—Cu3—I1	118.90 (4)	C9—C10—H10	119.5
O1ⁱ—Cu3—I4ⁱⁱ	106.23 (18)	C11—C10—H10	119.5
I3—Cu3—I4ⁱⁱ	105.84 (4)	C12—C11—C10	118.7 (9)
I1—Cu3—I4ⁱⁱ	107.65 (4)	C12—C11—H11	120.7
O1ⁱ—Cu3—Cu1	132.47 (18)	C10—C11—H11	120.7
I3—Cu3—Cu1	60.23 (3)	C11—C12—C13	122.0 (8)
I1—Cu3—Cu1	58.78 (3)	C11—C12—H12	119.0
I4ⁱⁱ—Cu3—Cu1	121.23 (5)	C13—C12—H12	119.0
O2ⁱⁱⁱ—Cu4—I4	106.57 (17)	O1—C13—N1	117.8 (8)
O2ⁱⁱⁱ—Cu4—I3^iv	120.84 (17)	O1—C13—C12	126.5 (7)
I4—Cu4—I3^iv	105.37 (4)	N1—C13—C12	115.6 (8)
O2ⁱⁱⁱ—Cu4—Cu2	121.72 (17)	C19—C14—C15	110.6 (7)
I4—Cu4—Cu2	58.77 (3)	C19—C14—H14A	109.5
I3^iv—Cu4—Cu2	117.37 (5)	C15—C14—H14A	109.5
O2ⁱⁱⁱ—Cu4—I2	101.65 (17)	C19—C14—H14B	109.5
I4—Cu4—I2	117.31 (4)	C15—C14—H14B	109.5
I3^iv—Cu4—I2	105.88 (4)	H14A—C14—H14B	108.1
Cu2—Cu4—I2	58.69 (4)	C16—C15—C14	110.0 (8)
Cu3—I1—Cu1	62.47 (3)	C16—C15—H15A	109.7
Cu3—I1—Cu2	107.56 (4)	C14—C15—H15A	109.7
Cu1—I1—Cu2	73.38 (4)	C16—C15—H15B	109.7
Cu2—I2—Cu1	74.17 (4)	C14—C15—H15B	109.7
Cu2—I2—Cu4	60.65 (3)	H15A—C15—H15B	108.2
Cu1—I2—Cu4	113.57 (4)	C17—C16—C15	112.1 (8)
Cu3—I3—Cu4ⁱⁱ	74.12 (4)	C17—C16—H16A	109.2
Cu3—I3—Cu1	62.16 (4)	C15—C16—H16A	109.2
Cu4ⁱⁱ—I3—Cu1	99.33 (4)	C17—C16—H16B	109.2
Cu2—I4—Cu4	61.89 (4)	C15—C16—H16B	109.2
Cu2—I4—Cu3^iv	107.19 (4)	H16A—C16—H16B	107.9
Cu4—I4—Cu3^iv	73.74 (4)	C16—C17—C18	112.0 (8)
C7—S1—C6	103.4 (4)	C16—C17—H17A	109.2
C7—S1—Cu1	106.5 (3)	C18—C17—H17A	109.2
C6—S1—Cu1	110.8 (3)	C16—C17—H17B	109.2
C20—S2—C19	104.0 (4)	C18—C17—H17B	109.2
C20—S2—Cu2	109.5 (3)	H17A—C17—H17B	107.9
C19—S2—Cu2	111.5 (3)	C19—C18—C17	110.5 (8)
C13—O1—Cu3ⁱⁱⁱ	127.4 (5)	C19—C18—H18A	109.5
C26—O2—Cu4ⁱ	126.2 (5)	C17—C18—H18A	109.5
C9—N1—C13	122.6 (8)	C19—C18—H18B	109.5
C9—N1—C8	119.6 (8)	C17—C18—H18B	109.5
C13—N1—C8	117.8 (7)	H18A—C18—H18B	108.1
C22—N2—C26	122.1 (7)	C18—C19—C14	110.9 (7)
C22—N2—C21	119.3 (7)	C18—C19—S2	111.6 (7)
C26—N2—C21	118.6 (7)	C14—C19—S2	105.6 (6)
C2—C1—C6	111.1 (7)	C18—C19—H19	109.6
C2—C1—H1A	109.4	C14—C19—H19	109.6
C6—C1—H1A	109.4	S2—C19—H19	109.6
C2—C1—H1B	109.4	C21—C20—S2	114.5 (6)
C6—C1—H1B	109.4	C21—C20—H20A	108.6
H1A—C1—H1B	108.0	S2—C20—H20A	108.6
C1—C2—C3	111.3 (7)	C21—C20—H20B	108.6
C1—C2—H2A	109.4	S2—C20—H20B	108.6
C3—C2—H2A	109.4	H20A—C20—H20B	107.6
C1—C2—H2B	109.4	N2—C21—C20	108.9 (6)
C3—C2—H2B	109.4	N2—C21—H21A	109.9
H2A—C2—H2B	108.0	C20—C21—H21A	109.9
C2—C3—C4	110.3 (7)	N2—C21—H21B	109.9
C2—C3—H3A	109.6	C20—C21—H21B	109.9
C4—C3—H3A	109.6	H21A—C21—H21B	108.3
C2—C3—H3B	109.6	C23—C22—N2	121.5 (9)
C4—C3—H3B	109.6	C23—C22—H22	119.2
H3A—C3—H3B	108.1	N2—C22—H22	119.2
C5—C4—C3	111.3 (7)	C22—C23—C24	119.1 (9)
C5—C4—H4A	109.4	C22—C23—H23	120.4
C3—C4—H4A	109.4	C24—C23—H23	120.4
C5—C4—H4B	109.4	C25—C24—C23	120.1 (8)
C3—C4—H4B	109.4	C25—C24—H24	120.0
H4A—C4—H4B	108.0	C23—C24—H24	120.0
C6—C5—C4	111.1 (7)	C24—C25—C26	121.2 (8)
C6—C5—H5A	109.4	C24—C25—H25	119.4
C4—C5—H5A	109.4	C26—C25—H25	119.4
C6—C5—H5B	109.4	O2—C26—N2	119.0 (7)
C4—C5—H5B	109.4	O2—C26—C25	125.0 (8)
H5A—C5—H5B	108.0	N2—C26—C25	116.0 (7)

C6—C1—C2—C3	57.6 (10)	C19—C14—C15—C16	56.2 (10)
C1—C2—C3—C4	−56.0 (10)	C14—C15—C16—C17	−55.8 (11)
C2—C3—C4—C5	54.9 (10)	C15—C16—C17—C18	55.6 (11)
C3—C4—C5—C6	−55.4 (10)	C16—C17—C18—C19	−55.2 (11)
C4—C5—C6—C1	56.1 (9)	C17—C18—C19—C14	55.8 (10)
C4—C5—C6—S1	176.2 (6)	C17—C18—C19—S2	173.2 (6)
C2—C1—C6—C5	−57.2 (9)	C15—C14—C19—C18	−57.1 (10)
C2—C1—C6—S1	−179.8 (6)	C15—C14—C19—S2	−178.1 (6)
C7—S1—C6—C5	63.5 (6)	C20—S2—C19—C18	58.8 (7)
Cu1—S1—C6—C5	177.3 (5)	Cu2—S2—C19—C18	176.7 (6)
C7—S1—C6—C1	−174.7 (6)	C20—S2—C19—C14	179.3 (5)
Cu1—S1—C6—C1	−60.9 (6)	Cu2—S2—C19—C14	−62.8 (6)
C6—S1—C7—C8	−154.7 (6)	C19—S2—C20—C21	62.3 (7)
Cu1—S1—C7—C8	88.4 (6)	Cu2—S2—C20—C21	−57.0 (6)
C9—N1—C8—C7	104.3 (8)	C22—N2—C21—C20	−101.2 (8)
C13—N1—C8—C7	−77.0 (9)	C26—N2—C21—C20	76.9 (8)
S1—C7—C8—N1	−179.3 (6)	S2—C20—C21—N2	174.1 (5)
C13—N1—C9—C10	−1.3 (13)	C26—N2—C22—C23	1.4 (12)
C8—N1—C9—C10	177.3 (8)	C21—N2—C22—C23	179.4 (8)
N1—C9—C10—C11	0.4 (14)	N2—C22—C23—C24	−0.1 (13)
C9—C10—C11—C12	0.2 (15)	C22—C23—C24—C25	0.0 (13)
C10—C11—C12—C13	0.1 (14)	C23—C24—C25—C26	−1.2 (13)
Cu3ⁱⁱⁱ—O1—C13—N1	165.9 (5)	Cu4ⁱ—O2—C26—N2	−179.4 (5)
Cu3ⁱⁱⁱ—O1—C13—C12	−15.3 (13)	Cu4ⁱ—O2—C26—C25	1.9 (12)
C9—N1—C13—O1	−179.5 (7)	C22—N2—C26—O2	178.8 (7)
C8—N1—C13—O1	1.9 (11)	C21—N2—C26—O2	0.8 (10)
C9—N1—C13—C12	1.6 (12)	C22—N2—C26—C25	−2.4 (11)
C8—N1—C13—C12	−177.1 (7)	C21—N2—C26—C25	179.6 (7)
C11—C12—C13—O1	−179.8 (9)	C24—C25—C26—O2	−179.0 (8)
C11—C12—C13—N1	−0.9 (13)	C24—C25—C26—N2	2.3 (12)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N2/C22–C26 ring

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···I4ⁱⁱ	0.99	3.26	4.107 (8)	145
C12—H12···I1ⁱⁱⁱ	0.95	3.30	3.899 (8)	123
C21—H21B···I3^iv	0.99	3.08	3.923 (8)	144
C5—H5A···Cg1^v	0.99	3.00	3.948 (9)	162

Symmetry codes: (ii) x−1, y, z; (iii) x, y−1, z; (iv) x+1, y, z; (v) x−1, y−1, z.

Funding information

This research was supported by the Basic Science Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2015R1D1A4A01020317 and 2017R1D1A3A03000534).

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

A two-dimensional copper(I) coordination polymer based on 1-[2-(cyclo­hexyl­sulfan­yl)eth­yl]pyridin-2(1H)-one

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Funding information

References

research communications

A two-dimensional copper(I) coordination polymer based on 1-[2-(cyclohexylsulfanyl)ethyl]pyridin-2(1H)-one

3. Supramolecular features