Syntheses and crystal structures of two copper(I)–halide π,σ-coordination compounds based on 2-[(prop-2-en-1-yl)sulfan­yl]pyridine

Slyvka, Y.; Pokhodylo, N.T.; Goreshnik, E.; Pavlyuk, O.; Mys'kiv, M.

doi:10.1107/S2056989021011002

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ISSN: 2056-9890

Volume 77| Part 11| November 2021| Pages 1180-1184

https://doi.org/10.1107/S2056989021011002

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Syntheses and crystal structures of two copper(I)–halide π,σ-coordination compounds based on 2-[(prop-2-en-1-yl)sulfanyl]pyridine

Yurii Slyvka,^a Nazariy T. Pokhodylo,^b ^* Evgeny Goreshnik,^c Olexii Pavlyuk ^a and Marian Mys'kiv ^a

^aDepartment of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodiya, 6, Lviv, 79005, Ukraine, ^bDepartment of Organic Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodiya, 6, Lviv, 79005, Ukraine, and ^cDepartment of Inorganic Chemistry and Technology, Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
^*Correspondence e-mail: pokhodylo@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 October 2021; accepted 21 October 2021; online 29 October 2021)

The title compounds, di-μ-chlorido-bis({2-[(η-2,3)-(prop-2-en-1-yl)sulfanyl]pyridine-κN}copper(I)), [Cu₂Cl₂(C₈H₉NS)₂], and di-μ-bromido-bis({2-[(η-2,3)-(prop-2-en-1-yl)sulfanyl]pyridine-κN}copper(I)), [Cu₂Br₂(C₈H₉NS)₂], were obtained by alternating-current electrochemical synthesis starting from an ethanolic solution of 2-[(prop-2-en-1-yl)sulfanyl]pyridine (Psup) and the copper(II) halide. The isostructural crystals are built up from centrosymmetric [Cu₂Hal₂(Psup)₂] dimers, which are formed due to the π,σ-chelating behavior of the organic ligand. In the crystals, the dimers are linked by C—H⋯Hal hydrogen bonds as well as by aromatic π–π stacking interactions into a three-dimensional network.

Keywords: copper(I); η²-interaction; pyridine-2-thiol; allyl derivative; crystal structure.

CCDC references: 2116969; 2116968

1. Chemical context

Cu-containing complexes have been found very promising regarding their catalytic activities in organic syntheses, non-linear optical properties and fluorescent activity (Wang et al., 2005 ; Yoshikai & Nakamura, 2012 ; Slyvka et al., 2018a ; Fedorchuk et al., 2020 ). Copper complexes also exhibit considerable biochemical activities, ranging from antibacterial and anti-inflammatory properties to cytostatic and enzyme inhibitory (Iakovidis et al., 2011 ; Tisato et al., 2010 ). Some of these compounds have been tested in vitro as potential anticancer drugs and found to be effective against A549 adenocarcinoma cells that are resistant to the widely used anticancer drug cisplatin (Marzano et al., 2006 ). It is worth noting that copper is an essential trace element with vital roles in many metalloenzymes participating in intracellular processes under normal and pathological conditions (Iakovidis et al., 2011).

Over the last two decades, increased interest has also been devoted to the crystal engineering of copper(I)–olefin complexes with allyl derivatives of heterocyclic compounds (Goreshnik et al., 2011 ; Slyvka et al., 2013 ; Hordiichuk et al., 2019 ). The presence of a C=C olefin bond in a substituent attached to the heterocyclic ring may serve as a key feature for the selective coordination of transition-metal ions due to metal–olefin π-bonding (Rourke, 2006 ; Slyvka et al., 2013; Kowalska et al., 2021 ). Allyl derivatives of some heterocyclic compounds were found to be suitable for the preparation of π-coordination compounds with Cu^I salts that are unknown (or less stable) in the free state. For instance, the first examples of Cu(C₆H₅SO₃), Cu(p-CH₃C₆H₄SO₃) or CuHSO₄ π-complexes as well as the direct Cu^I⋯F(SiF₆^2–) interaction have been observed in copper(I) π-compounds with allyl derivatives of triazole and thiadiazole (Goreshnik et al., 2016 ; Ardan et al., 2017 ; Slyvka et al., 2018b ; Fedorchuk et al., 2020 ). N-Allyl derivatives of pyridine were found to be suitable ligands for the crystal engineering of Cu^I coordination compounds with inorganic fragments of different complexibility and related to the pK_a values of the initial pyridine bases (Goreshnik et al., 2003 ; Pavlyuk et al., 2005 ). Taking into account the fact that allylsulfanyl derivatives of pyridine have not been investigated for their coordination behavior regarding copper(I), in this work we present the synthesis and structural characterization of two novel copper(I) halide π-coordination compounds [Cu₂Cl₂(Psup)₂] (I) & [Cu₂Br₂(Psup)₂] (II) with 2-[(prop-2-en-1-yl)sulfanyl]pyridine (Psup), C₈H₉NS.

2. Structural commentary

The title compounds are isostructural and crystallize in the centrosymmetric space group P2₁/c with one Psup organic molecule, one copper(I) ion and one halide ion in the asymmetric unit. As shown in Figs. 1 and 2, these structures are constructed from centrosymmetric [Cu₂Hal₂(Psup)₂] [Hal = Cl (I) or Br (II)] dimers, which are formed due to the chelating behavior of the organic ligand. A close to trigonal–pyramidal coordination environment of the Cu^I cation includes the η² allylic C=C bond, the pyridine N atom and a Hal1 ion in the basal plane (Tables 1 and 2). The apical position of the Cu^I polyhedron is occupied by the Hal1ⁱ [symmetry code: (i) −x + 1, −y + 1, −z + 1) ion at 2.6186 (9) Å in I and at 2.7113 (6) Å in II. The corresponding four-coordinate geometry indices τ₄ (Yang et al., 2007 ) are 0.81 (I) and 0.83 (II). For comparison, in the structures of previously studied CuCl and CuBr π,σ-complexes with allylacetoneoxime, the Cu—Hal_ap distances are slightly higher at 2.719 (5) and 2.778 (4) Å (Filinchuk et al., 1998 ).

Table 1
Selected bond lengths (Å) for I

Cu1—Cl1	2.2691 (9)	Cu1—C8	2.037 (3)
Cu1—Cl1ⁱ	2.6186 (9)	Cu1—C9	2.052 (3)
Cu1—N1	2.026 (2)
Symmetry code: (i) .

Table 2
Selected bond lengths (Å) for II

Cu1—Br1	2.4097 (6)	Cu1—C8	2.048 (4)
Cu1—Br1ⁱ	2.7113 (6)	Cu1—C9	2.065 (4)
Cu1—N1	2.025 (3)
Symmetry code: (i) .

Figure 1
The molecular structure of I with displacement ellipsoids drawn at the 50% probability level. Symmetry code: (i) −x + 1, −y + 1, −z + 1.

Figure 2
The molecular structure of II with displacement ellipsoids drawn at the 50% probability level. Symmetry code: (i) −x + 1, −y + 1, −z + 1.

Being π-connected to the metal center, the C8=C9 bond of the ligand is elongated due to back-donation from an occupied 3d metal orbital to a low-lying empty π*-orbital of the olefin to 1.364 (4) Å (I) and to 1.354 (6) Å (II) in comparison with an uncoordinated allylic C=C bond (Slyvka et al., 2021 ). The allylsulfanyl group in (I) and (II) has synclinal conformation relative to the S1—C7 bond and an antiperiplanar conformation relative to the C7—C8 bond [the corresponding torsion angles C2—S1—C7—C8 and S1—C7—C8—C9 are 68.1 (3) and −152.1 (3)°, respectively, in I and 68.3 (3) and −151.7 (3)°(II)].

3. Supramolecular features

As shown in Fig. 3 and listed in Tables 3 and 4, the crystal structures of (I) and (II) features several weak intermolecular interactions. The hydrogen atom H6 of the pyridine ring participates in an intramolecular C—H⋯Hal bond with the Hal ion of the inorganic subunit. The other hydrogen atom H6 of the pyridine ring and the methylene hydrogen atom H7B of the allylsulfanyl substituent are involved in intermolecular C—H⋯Hal bonding, linking the dimeric moieties into a three-dimensional network. The pyridine rings of adjacent dimers are also involved in face-to-face π–π stacking interactions with a centroid–centroid separation of 3.680 (4) Å in I and 3.693 (4) Å in II. The unit-cell packing for (I) is shown in Fig. 4.

Table 3
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl1ⁱⁱ	0.95	2.91	3.581 (3)	129
C6—H6⋯Cl1	0.95	2.80	3.447 (3)	126
C7—H7B⋯Cl1ⁱⁱⁱ	0.99	2.89	3.676 (3)	137
Symmetry codes: (ii) x+1, y, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 4
Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Br1ⁱⁱ	0.95	3.02	3.696 (4)	129
C6—H6⋯Br1	0.95	2.94	3.576 (4)	126
C7—H7B⋯Br1ⁱⁱⁱ	0.99	2.94	3.744 (4)	139
Symmetry codes: (ii) x+1, y, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
Fragment of the extended structure of I with hydrogen bonds shown as dashed lines. Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x + 1, y, z; (iii) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) x, −y + $[{3\over 2}]$ , −z + $[{1\over 2}]$ . The packing for II is essentially identical.

Figure 4
A view along the a-axis direction of the crystal packing of I.

4. Database survey

The most closest related compounds to the title compounds, containing a similar {Cu₂Hal₂} dimer in which a π,σ-chelating ligand is bound to copper(I) are: di-μ-chlorobis[(1-allyl-3,5-dimethylpyrazole)copper(I)] (III) [Cambridge Structural Database (Version 2021.1; Groom et al., 2016 ) refcode ALMPCU; Fukushima et al., 1976 ], bis(μ₂-chloro)-bis(η²-allylacetoneoxime-N)dicopper(I) (IV) (GOKYAG; Filinchuk et al., 1998), bis(μ₂-bromo)-bis(η²-allylacetoneoxime-N)dicopper(I) (V) (GOKYEK; Filinchuk et al., 1998), bis[(μ₂-bromo)(η²-2-(allylthio)benzimidazole-N)copper(I)] (VI) (WUCRAN; Goreshnik et al., 2002 ) and bis{(μ₂-iodo)[(η²-allyl)(2-pyridyl)dimethylsilane]copper} (VII) (XAZGIP; Kamei et al., 2005 ).

Compounds (III) and (VII) crystallize in the triclinic crystal system in space group P $[\overline{1}]$ . Compounds (IV), (V) and (VI) crystallize in the monoclinic crystal system in space group P2₁/c (settings P2₁/a, P2₁/c and P2₁/n, respectively). Structures (III), (IV), (V) and (VI) are built up from centrosymmetric [Cu₂Hal₂(Ligand)₂] dimers. In the compounds bis[(μ₂-chloro)chloro(η²-1-allyl-2-aminopyridinium)copper(I)] (XIII) (BEBFOE) and bis[(μ₂-chloro)bromo(η²-1-allyl-2-aminopyridinium)copper(I)] (IX) (BEBGAR; Goreshnik et al., 2003), the 1-allyl-2-aminopyridinium cation acts as a monodentate π-ligand, being attached to the centrosymmetic anionic {Cu₂Hal₄}²⁻ part through the allylic C=C bond. An analogous monodentate 1-allylpyridinium cation in the structure of catena-[bis(μ₃-chloro)bis(μ₂-chloro)bis(η²-1-allylpyridinium)dichlorotetracopper(I)] (X) (YAPQIQ; Pavlyuk et al., 2005) forces the realization of an infinite {Cu₄Cl₄}_n inorganic chain.

5. Synthesis and crystallization

Crystals of the title compounds were obtained under conditions of alternating-current electrochemical synthesis (Slyvka et al., 2018a) starting from an ethanolic solution of 2-[(prop-2-en-1-yl)sulfanyl]pyridine (Psup) and the copper(II) halide. For this, a solution of Psup (1.5 mmol, 0.227 g) in 2.0 ml of 96% ethanol was added to a solution of CuCl₂·2H₂O (1.6 mmol, 0.273 g) or CuBr₂ (1.6 mmol, 0.357 g) in 3.0 ml of 96% ethanol. The mixture was carefully stirred and then was placed into a small 5.5 ml test tube. A copper wire was wrapped into a spiral of 1 cm diameter. A straight copper wire was placed inside the spiral. These copper electrodes were inserted in a cork and immersed in the aforementioned mixture. The mixture was subjected to alternating current reduction (frequency 50 Hz, voltage 0.45 V) and after 3–4 days, good-quality slightly yellowish crystals of the title compounds appeared on the copper wire electrodes. Compound I: yield 12%, m.p. 413 K; compound II: yield 8%, m.p. 407 K.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. All H atoms were positioned geometrically with C—H = 0.95–0.99 Å and refined as riding atoms. The constraint U_iso(H) = 1.2U_eq(C) was applied in all cases.

Table 5
Experimental details

	I	II
Crystal data
Chemical formula	[Cu₂Cl₂(C₈H₉NS)₂]	[Cu₂Br₂(C₈H₉NS)₂]
M_r	500.42	589.34
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	150	150
a, b, c (Å)	9.2729 (16), 9.5740 (13), 11.037 (2)	9.5009 (6), 9.6022 (5), 11.0936 (8)
β (°)	108.52 (2)	107.257 (7)
V (Å³)	929.1 (3)	966.50 (11)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	2.80	6.55
Crystal size (mm)	0.33 × 0.28 × 0.19	0.44 × 0.35 × 0.22

Data collection
Diffractometer	Rigaku New Gemini, Dual, Atlas	Rigaku New Gemini, Dual, Atlas
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ )	Analytical (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ )
T_min, T_max	0.546, 0.693	0.191, 0.368
No. of measured, independent and observed [I > 2σ(I)] reflections	8088, 2161, 1730	6837, 2162, 1854
R_int	0.058	0.044
(sin θ/λ)_max (Å⁻¹)	0.686	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.077, 1.08	0.034, 0.079, 1.08
No. of reflections	2161	2162
No. of parameters	109	109
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.64	0.82, −0.75
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 2116969; 2116968

Crystal structure: contains datablocks I, II, publication_text. DOI: https://doi.org/10.1107/S2056989021011002/hb7993sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011002/hb7993Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989021011002/hb7993IIsup3.hkl

checkCIF report

Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Di-µ-chlorido-bis({2-[(η-2,3)-(prop-2-en-1-yl)sulfanyl]pyridine-κN}copper(I)) (I) top

Crystal data top

[Cu₂Cl₂(C₈H₉NS)₂]	F(000) = 504
M_r = 500.42	D_x = 1.789 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.2729 (16) Å	Cell parameters from 3255 reflections
b = 9.5740 (13) Å	θ = 3.8–28.9°
c = 11.037 (2) Å	µ = 2.80 mm⁻¹
β = 108.52 (2)°	T = 150 K
V = 929.1 (3) Å³	Irregular, yellowish
Z = 2	0.33 × 0.28 × 0.19 mm

Data collection top

New Gemini, Dual, Cu at home/near, Atlas diffractometer	1730 reflections with I > 2σ(I)
Detector resolution: 10.6426 pixels mm^-1	R_int = 0.058
ω scans	θ_max = 29.2°, θ_min = 2.9°
Absorption correction: analytical (CrysalisPro; Rigaku OD, 2021)	h = −12→12
T_min = 0.546, T_max = 0.693	k = −12→11
8088 measured reflections	l = −15→15
2161 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0228P)² + 0.6316P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2161 reflections	Δρ_max = 0.51 e Å⁻³
109 parameters	Δρ_min = −0.64 e Å⁻³
0 restraints

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
Cu1	0.57740 (4)	0.64590 (4)	0.46958 (4)	0.01225 (12)
Cl1	0.36070 (8)	0.54060 (8)	0.34752 (7)	0.01340 (18)
S1	0.91865 (9)	0.82046 (8)	0.47781 (8)	0.01693 (19)
N1	0.7401 (3)	0.5908 (2)	0.3922 (2)	0.0098 (5)
C2	0.8718 (3)	0.6558 (3)	0.4035 (3)	0.0113 (6)
C3	0.9837 (3)	0.5968 (3)	0.3594 (3)	0.0142 (7)
H3	1.075431	0.645998	0.368256	0.017*
C4	0.9603 (4)	0.4679 (3)	0.3036 (3)	0.0175 (7)
H4	1.036450	0.425281	0.275400	0.021*
C5	0.8239 (4)	0.4003 (3)	0.2888 (3)	0.0158 (7)
H5	0.803694	0.311139	0.249195	0.019*
C6	0.7184 (3)	0.4656 (3)	0.3331 (3)	0.0145 (7)
H6	0.624182	0.419633	0.321361	0.017*
C7	0.7410 (4)	0.8972 (3)	0.4778 (3)	0.0145 (7)
H7A	0.759319	0.996020	0.504812	0.017*
H7B	0.669754	0.896375	0.389294	0.017*
C8	0.6665 (4)	0.8249 (3)	0.5633 (3)	0.0137 (7)
H8	0.729407	0.776905	0.636305	0.016*
C9	0.5133 (4)	0.8248 (3)	0.5412 (3)	0.0198 (8)
H9A	0.447951	0.872113	0.468765	0.024*
H9B	0.471792	0.777530	0.598143	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0103 (2)	0.0106 (2)	0.0177 (2)	−0.00093 (15)	0.00702 (17)	−0.00293 (16)
Cl1	0.0082 (4)	0.0164 (4)	0.0146 (4)	−0.0007 (3)	0.0022 (3)	0.0002 (3)
S1	0.0130 (4)	0.0140 (4)	0.0249 (5)	−0.0034 (3)	0.0076 (4)	−0.0022 (3)
N1	0.0066 (12)	0.0092 (12)	0.0125 (13)	0.0009 (10)	0.0013 (11)	0.0005 (11)
C2	0.0131 (15)	0.0132 (15)	0.0063 (14)	0.0031 (13)	0.0013 (13)	0.0022 (12)
C3	0.0097 (15)	0.0187 (17)	0.0160 (16)	0.0024 (13)	0.0064 (13)	0.0057 (14)
C4	0.0147 (16)	0.0270 (19)	0.0129 (16)	0.0101 (14)	0.0073 (14)	0.0026 (15)
C5	0.0192 (17)	0.0145 (16)	0.0128 (16)	0.0050 (14)	0.0037 (14)	−0.0029 (13)
C6	0.0117 (15)	0.0160 (16)	0.0162 (16)	0.0010 (13)	0.0049 (14)	0.0018 (13)
C7	0.0176 (17)	0.0091 (15)	0.0184 (16)	−0.0004 (13)	0.0079 (14)	−0.0004 (13)
C8	0.0182 (17)	0.0080 (15)	0.0154 (16)	−0.0003 (13)	0.0059 (14)	−0.0017 (13)
C9	0.0245 (19)	0.0091 (16)	0.031 (2)	0.0003 (14)	0.0164 (16)	−0.0026 (14)

Geometric parameters (Å, º) top

Cu1—Cl1	2.2691 (9)	C4—H4	0.9500
Cu1—Cl1ⁱ	2.6186 (9)	C4—C5	1.383 (4)
Cu1—N1	2.026 (2)	C5—H5	0.9500
Cu1—C8	2.037 (3)	C5—C6	1.375 (4)
Cu1—C9	2.052 (3)	C6—H6	0.9500
S1—C2	1.766 (3)	C7—H7A	0.9900
S1—C7	1.804 (3)	C7—H7B	0.9900
N1—C2	1.340 (4)	C7—C8	1.503 (4)
N1—C6	1.349 (4)	C8—H8	0.9500
C2—C3	1.397 (4)	C8—C9	1.364 (4)
C3—H3	0.9500	C9—H9A	0.9500
C3—C4	1.366 (4)	C9—H9B	0.9500

Cl1—Cu1—Cl1ⁱ	95.20 (3)	C4—C5—H5	120.9
N1—Cu1—Cl1ⁱ	97.91 (7)	C6—C5—C4	118.1 (3)
N1—Cu1—Cl1	105.77 (7)	C6—C5—H5	120.9
N1—Cu1—C8	101.34 (11)	N1—C6—C5	124.2 (3)
N1—Cu1—C9	136.50 (12)	N1—C6—H6	117.9
C8—Cu1—Cl1ⁱ	103.19 (9)	C5—C6—H6	117.9
C8—Cu1—Cl1	144.63 (9)	S1—C7—H7A	108.7
C8—Cu1—C9	38.96 (12)	S1—C7—H7B	108.7
C9—Cu1—Cl1ⁱ	106.96 (10)	H7A—C7—H7B	107.6
C9—Cu1—Cl1	106.81 (10)	C8—C7—S1	114.4 (2)
Cu1—Cl1—Cu1ⁱ	84.80 (3)	C8—C7—H7A	108.7
C2—S1—C7	105.89 (15)	C8—C7—H7B	108.7
C2—N1—Cu1	128.2 (2)	Cu1—C8—H8	93.7
C2—N1—C6	116.7 (3)	C7—C8—Cu1	105.2 (2)
C6—N1—Cu1	114.72 (19)	C7—C8—H8	118.4
N1—C2—S1	122.7 (2)	C9—C8—Cu1	71.15 (18)
N1—C2—C3	122.3 (3)	C9—C8—C7	123.2 (3)
C3—C2—S1	115.0 (2)	C9—C8—H8	118.4
C2—C3—H3	120.2	Cu1—C9—H9A	105.0
C4—C3—C2	119.5 (3)	Cu1—C9—H9B	94.9
C4—C3—H3	120.2	C8—C9—Cu1	69.90 (18)
C3—C4—H4	120.5	C8—C9—H9A	120.0
C3—C4—C5	119.0 (3)	C8—C9—H9B	120.0
C5—C4—H4	120.5	H9A—C9—H9B	120.0

Cu1—N1—C2—S1	−7.6 (4)	C2—C3—C4—C5	1.8 (5)
Cu1—N1—C2—C3	171.1 (2)	C3—C4—C5—C6	−1.0 (5)
Cu1—N1—C6—C5	−171.2 (2)	C4—C5—C6—N1	−1.1 (5)
S1—C2—C3—C4	178.2 (2)	C6—N1—C2—S1	179.9 (2)
S1—C7—C8—Cu1	−75.0 (2)	C6—N1—C2—C3	−1.4 (4)
S1—C7—C8—C9	−152.1 (3)	C7—S1—C2—N1	−19.4 (3)
N1—C2—C3—C4	−0.6 (5)	C7—S1—C2—C3	161.8 (2)
C2—S1—C7—C8	68.1 (3)	C7—C8—C9—Cu1	96.2 (3)
C2—N1—C6—C5	2.3 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱⁱ	0.95	2.91	3.581 (3)	129
C6—H6···Cl1	0.95	2.80	3.447 (3)	126
C7—H7B···Cl1ⁱⁱⁱ	0.99	2.89	3.676 (3)	137

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

Di-µ-bromido-bis({2-[(η-2,3)-(prop-2-en-1-yl)sulfanyl]pyridine-κN}copper(I)) (II) top

Crystal data top

[Cu₂Br₂(C₈H₉NS)₂]	F(000) = 576
M_r = 589.34	D_x = 2.025 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.5009 (6) Å	Cell parameters from 3535 reflections
b = 9.6022 (5) Å	θ = 3.1–29.0°
c = 11.0936 (8) Å	µ = 6.55 mm⁻¹
β = 107.257 (7)°	T = 150 K
V = 966.50 (11) Å³	Irregular, yellowish
Z = 2	0.44 × 0.35 × 0.22 mm

Data collection top

New Gemini, Dual, Cu at home/near, Atlas diffractometer	1854 reflections with I > 2σ(I)
Detector resolution: 10.6426 pixels mm^-1	R_int = 0.044
ω scans	θ_max = 29.0°, θ_min = 2.9°
Absorption correction: analytical (CrysalisPro; Rigaku OD, 2021)	h = −12→12
T_min = 0.191, T_max = 0.368	k = −10→12
6837 measured reflections	l = −12→13
2162 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0328P)² + 1.3651P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2162 reflections	Δρ_max = 0.82 e Å⁻³
109 parameters	Δρ_min = −0.74 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Br1	0.36045 (4)	0.54960 (3)	0.34080 (3)	0.01538 (12)
Cu1	0.58645 (5)	0.64663 (4)	0.47542 (4)	0.01478 (13)
S1	0.91726 (10)	0.82315 (9)	0.48313 (10)	0.0201 (2)
N1	0.7467 (3)	0.5936 (3)	0.3976 (3)	0.0135 (6)
C2	0.8735 (4)	0.6601 (3)	0.4079 (3)	0.0127 (7)
C3	0.9838 (4)	0.6033 (4)	0.3631 (3)	0.0176 (8)
H3	1.072777	0.652922	0.372109	0.021*
C4	0.9622 (4)	0.4747 (4)	0.3060 (4)	0.0191 (8)
H4	1.036808	0.433779	0.276414	0.023*
C5	0.8301 (4)	0.4056 (4)	0.2920 (3)	0.0186 (8)
H5	0.811443	0.317584	0.251361	0.022*
C6	0.7270 (4)	0.4681 (4)	0.3387 (4)	0.0168 (8)
H6	0.636629	0.420650	0.329185	0.020*
C7	0.7453 (4)	0.8986 (4)	0.4850 (4)	0.0171 (8)
H7A	0.762903	0.996856	0.512413	0.021*
H7B	0.677805	0.898701	0.397736	0.021*
C8	0.6700 (4)	0.8262 (4)	0.5692 (4)	0.0192 (8)
H8	0.729668	0.778274	0.641149	0.023*
C9	0.5222 (5)	0.8253 (4)	0.5484 (4)	0.0247 (9)
H9A	0.459626	0.872317	0.477213	0.030*
H9B	0.481069	0.777660	0.605052	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01321 (19)	0.0189 (2)	0.0130 (2)	−0.00013 (14)	0.00236 (14)	0.00135 (13)
Cu1	0.0151 (2)	0.0135 (2)	0.0174 (3)	−0.00122 (17)	0.00731 (19)	−0.00381 (16)
S1	0.0185 (5)	0.0159 (5)	0.0268 (5)	−0.0045 (4)	0.0081 (4)	−0.0043 (4)
N1	0.0154 (15)	0.0150 (14)	0.0108 (15)	0.0022 (12)	0.0048 (12)	−0.0002 (11)
C2	0.0152 (18)	0.0151 (17)	0.0073 (17)	0.0006 (14)	0.0024 (14)	0.0040 (13)
C3	0.0165 (19)	0.0237 (19)	0.0136 (19)	−0.0004 (15)	0.0063 (15)	0.0019 (14)
C4	0.0192 (19)	0.023 (2)	0.016 (2)	0.0059 (16)	0.0066 (16)	0.0024 (15)
C5	0.021 (2)	0.0209 (19)	0.0142 (19)	0.0041 (15)	0.0054 (15)	−0.0011 (14)
C6	0.0167 (19)	0.0165 (18)	0.018 (2)	−0.0004 (15)	0.0058 (15)	−0.0007 (14)
C7	0.022 (2)	0.0116 (17)	0.019 (2)	−0.0006 (15)	0.0079 (16)	−0.0002 (14)
C8	0.030 (2)	0.0103 (17)	0.019 (2)	−0.0003 (15)	0.0101 (17)	−0.0027 (14)
C9	0.033 (2)	0.0115 (18)	0.036 (2)	−0.0004 (16)	0.020 (2)	−0.0065 (15)

Geometric parameters (Å, º) top

Cu1—Br1	2.4097 (6)	C4—H4	0.9500
Cu1—Br1ⁱ	2.7113 (6)	C4—C5	1.387 (5)
Cu1—N1	2.025 (3)	C5—H5	0.9500
Cu1—C8	2.048 (4)	C5—C6	1.374 (5)
Cu1—C9	2.065 (4)	C6—H6	0.9500
S1—C2	1.765 (4)	C7—H7A	0.9900
S1—C7	1.793 (4)	C7—H7B	0.9900
N1—C2	1.338 (5)	C7—C8	1.505 (5)
N1—C6	1.357 (5)	C8—H8	0.9500
C2—C3	1.397 (5)	C8—C9	1.354 (6)
C3—H3	0.9500	C9—H9A	0.9500
C3—C4	1.375 (5)	C9—H9B	0.9500

Cu1—Br1—Cu1ⁱ	82.521 (18)	C4—C5—H5	120.9
Br1—Cu1—Br1ⁱ	97.479 (19)	C6—C5—C4	118.1 (4)
N1—Cu1—Br1ⁱ	98.64 (8)	C6—C5—H5	120.9
N1—Cu1—Br1	106.43 (9)	N1—C6—C5	123.9 (4)
N1—Cu1—C8	101.60 (14)	N1—C6—H6	118.1
N1—Cu1—C9	136.30 (14)	C5—C6—H6	118.1
C8—Cu1—Br1ⁱ	104.22 (11)	S1—C7—H7A	108.5
C8—Cu1—Br1	141.26 (11)	S1—C7—H7B	108.5
C8—Cu1—C9	38.43 (15)	H7A—C7—H7B	107.5
C9—Cu1—Br1	104.57 (12)	C8—C7—S1	115.0 (3)
C9—Cu1—Br1ⁱ	107.05 (12)	C8—C7—H7A	108.5
C2—S1—C7	106.04 (17)	C8—C7—H7B	108.5
C2—N1—Cu1	128.0 (2)	Cu1—C8—H8	93.7
C2—N1—C6	117.2 (3)	C7—C8—Cu1	104.9 (2)
C6—N1—Cu1	114.5 (2)	C7—C8—H8	118.0
N1—C2—S1	122.9 (3)	C9—C8—Cu1	71.5 (2)
N1—C2—C3	122.3 (3)	C9—C8—C7	123.9 (4)
C3—C2—S1	114.7 (3)	C9—C8—H8	118.0
C2—C3—H3	120.3	Cu1—C9—H9A	104.7
C4—C3—C2	119.3 (4)	Cu1—C9—H9B	95.0
C4—C3—H3	120.3	C8—C9—Cu1	70.1 (2)
C3—C4—H4	120.4	C8—C9—H9A	120.0
C3—C4—C5	119.1 (4)	C8—C9—H9B	120.0
C5—C4—H4	120.4	H9A—C9—H9B	120.0

Cu1—N1—C2—S1	−6.5 (4)	C2—C3—C4—C5	1.2 (5)
Cu1—N1—C2—C3	171.5 (3)	C3—C4—C5—C6	−1.3 (6)
Cu1—N1—C6—C5	−172.5 (3)	C4—C5—C6—N1	0.1 (6)
S1—C2—C3—C4	178.3 (3)	C6—N1—C2—S1	−179.3 (3)
S1—C7—C8—Cu1	−74.2 (3)	C6—N1—C2—C3	−1.4 (5)
S1—C7—C8—C9	−151.7 (3)	C7—S1—C2—N1	−20.3 (3)
N1—C2—C3—C4	0.2 (5)	C7—S1—C2—C3	161.7 (3)
C2—S1—C7—C8	68.3 (3)	C7—C8—C9—Cu1	95.9 (3)
C2—N1—C6—C5	1.3 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Br1ⁱⁱ	0.95	3.02	3.696 (4)	129
C6—H6···Br1	0.95	2.94	3.576 (4)	126
C7—H7B···Br1ⁱⁱⁱ	0.99	2.94	3.744 (4)	139

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

Funding information

This work was supported by the Ministry of Education and Science of Ukraine (Grant Nos. 0120U101622 and 0120U102028) and the Slovenian Research Agency (ARRS) within the research program P1–0045 Inorganic Chemistry and Technology.

References

Ardan, B., Kinzhybalo, V., Slyvka, Y., Shyyka, O., Luk`yanov, M., Lis, T. & Mys`kiv, M. (2017). Acta Cryst. C73, 36–46. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fedorchuk, A. A., Slyvka, Yu. I., Goreshnik, E. A., Kityk, I. V., Czaja, P. & Mys'kiv, M. G. (2018). J. Mol. Struct. 1171, 644–649. CrossRef CAS Google Scholar
Fedorchuk, A., Goreshnik, E., Slyvka, Yu. & Mys'kiv, M. (2020). Acta Chim. Slov. 67, 1148–1154. CrossRef CAS PubMed Google Scholar
Filinchuk, Ya. E., Mys'kiv, M. G. & Davydov, V. N. (1998). Koord. Khim.(Russ.)(Coord. Chem.). 24, 771–775. Google Scholar
Fukushima, K., Kobayashi, A., Miyamoto, T. & Sasaki, Y. (1976). Bull. Chem. Soc. Jpn, 49, 143–146. CrossRef CAS Google Scholar
Goreshnik, E. A., Schollmeyer, D. & Myskiv, M. G. (2002). ZAAC, 628, 2118–2122. CAS Google Scholar
Goreshnik, E. A., Slyvka, Yu. I. & Mys'kiv, M. G. (2011). Inorg. Chim. Acta, 377, 177–180. Web of Science CSD CrossRef CAS Google Scholar
Goreshnik, E. A., Veryasov, G., Morozov, D., Slyvka, Yu., Ardan, B. & Mys'kiv, M. G. (2016). J. Organomet. Chem. 810, 1–11. Web of Science CSD CrossRef CAS Google Scholar
Goreshnik, E., Schollmeier, D. & Mys'kiv, M. (2003). Acta Cryst. C59, m478–m481. CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hordiichuk, O. R., Slyvka, Yu. I., Kinzhybalo, V. V., Goreshnik, E. A., Bednarchuk, T. J., Bednarchuk, O., Jedryka, J., Kityk, I. & Mys'kiv, M. G. (2019). Inorg. Chim. Acta, 495, 119012. CrossRef Google Scholar
Iakovidis, I., Delimaris, I. & Piperakis, S. M. (2011). Mol. Biol. Int. 2011, 1–13. CrossRef Google Scholar
Kamei, T., Fujita, K., Itami, K. & Yoshida, J. (2005). Org. Lett. 7, 4725–4728. CrossRef PubMed CAS Google Scholar
Kowalska, D. A., Kinzhybalo, V., Slyvka, Y. I. & Wołcyrz, M. (2021). Acta Cryst.. B77, 241–248. CrossRef IUCr Journals Google Scholar
Marzano, C., Pellei, M., Alidori, S., Brossa, A., Lobbia, G. G., Tisato, F. & Santini, C. (2006). J. Inorg. Biochem. 100, 299–304. CrossRef PubMed CAS Google Scholar
Pavlyuk, O. V., Goreshnik, E. A., Ciunik, Z. & Mys'kiv, M. G. (2005). ZAAC, 631, 793–797. CAS Google Scholar
Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan. Google Scholar
Rourke, J. (2006). Appl. Organomet. Chem. 20, 811–811. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Slyvka, Yu., Fedorchuk, A. A., Goreshnik, E., Lakshminarayana, G., Kityk, I. V., Czaja, P. & Mys'kiv, M. (2018b). Chem. Phys. Lett. 694, 112–119. CrossRef CAS Google Scholar
Slyvka, Yu., Goreshnik, E., Pavlyuk, O. & Mys'kiv, M. (2013). Open Chem. 11, 1875–1901. CrossRef CAS Google Scholar
Slyvka, Y., Kinzhybalo, V., Shyyka, O. & Mys'kiv, M. (2021). Acta Cryst. C77, 249–256. CrossRef IUCr Journals Google Scholar
Slyvka, Yu. I., Fedorchuk, A. A., Pokhodylo, N. T., Lis, T., Kityk, I. V. & Mys'kiv, M. G. (2018a). Polyhedron, 147, 86–93. CrossRef CAS Google Scholar
Tisato, F., Marzano, C., Porchia, M., Pellei, M. & Santini, C. (2010). Med. Res. Rev. 30, 708–749. Web of Science PubMed CAS Google Scholar
Wang, X.-S., Zhao, H., Li, Y.-H., Xiong, R.-G. & You, X.-Z. (2005). Top. Catal. 35, 43–61. Web of Science CrossRef Google Scholar
Yang, L., Powell, D. R. & Houser, R. P. (2007). Dalton Trans. pp. 955–964. Web of Science CSD CrossRef PubMed CAS Google Scholar
Yoshikai, N. & Nakamura, E. (2012). Chem. Rev. 112, 2339–2372. CrossRef CAS PubMed Google Scholar

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Volume 77| Part 11| November 2021| Pages 1180-1184

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

Syntheses and crystal structures of two copper(I)–halide π,σ-coordination compounds based on 2-[(prop-2-en-1-yl)sulfan­yl]pyridine

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

Syntheses and crystal structures of two copper(I)–halide π,σ-coordination compounds based on 2-[(prop-2-en-1-yl)sulfanyl]pyridine

3. Supramolecular features